CN1017726B - 加有磁场的微波等离子体化学汽相淀积法 - Google Patents

加有磁场的微波等离子体化学汽相淀积法

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CN1017726B
CN1017726B CN87107779A CN87107779A CN1017726B CN 1017726 B CN1017726 B CN 1017726B CN 87107779 A CN87107779 A CN 87107779A CN 87107779 A CN87107779 A CN 87107779A CN 1017726 B CN1017726 B CN 1017726B
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reaction chamber
magnetic field
substrate
microwave
magneticstrength
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犬岛乔
广濑直树
山崎舜平
田代卫
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Abstract

本说明书叙述了一种新型的化学汽相淀积法。这里化学汽相反应的主要的激发动力不是电子回旋共振(这时的电子作为独立粒子能够运动而不相互作用)而是混合回旋共振。在这种新提出的共振中，共振空间较大，因而用此新方法可将金刚石之类的高熔点物质淀积成薄膜状。

Description

本发明是关于加有磁场的微波等离子体化学汽淀积法。
最近电子回旋共振化学汽相淀积法（ECR CVD）作为制造薄膜，特别是非晶薄膜的新方法已引起研究人员们的兴趣。例如，松雄等人在美国专利4，401，054中就公开了一种这类ECR CVD设备。这种新技术应用微波借助于在激发区间中对等离子气体起箍缩作用的磁场将反应气体激发成等离子状态。利用这种组态，反应气体能吸收微波的能量。待涂敷的衬底安置在远离激发区间（共振区间）的地方以防衬底受到溅射。受激后的气体从共振区簇射到衬底上。为产生电子回旋共振，将共振区间中的压强维持在1.33×10-1至1.33×10-3帕，在此压强下，可以把电子视为独立的粒子，且以在磁场强度取电子回旋共振所需的磁场强度的表面上，这些电子以电子回旋共振的方式与微波产生共振。用发散磁场将激发过的等离子气体从共振区间引出到远离共振区配置有待涂敷的衬底的淀积区间。
要利用这类现有技术的方法制取多晶或单晶结构的薄膜是非常困难的，因此目前现有的方法几乎只局限于非晶薄膜的制造。此外按照这种现有技术是难以产生高能化学汽相反应的，因而不能在具有凹口和孔穴的均匀表面上形成金刚石薄膜或其它高熔点薄膜或均质薄膜。
因此本发明的一个目的是提供一种能制造现有技术所不能制造的薄膜（例如金刚石薄膜、或高熔点材料制成的薄膜）的加有磁场的微波等离子体化学汽相淀积法。
根据本发明的一个方面，待涂敷物体的表面系安置在微波电场处于最大值的共振区间的一个区域。在这种布局的情况下就可以边淀积边对 淀积出来的薄膜进行部分溅射，因而，举例说，可以制适金刚石薄膜。
根据本发明的另一个方面，一种新的化学汽相淀积法达到了登峰造极的水平。新方法应用了由本发明同人第一个获取的混合回旋共振。在这种新型的激发过程中，反应气体本身的相互作用应视为除磁场和微波之外还应加以考虑的不可忽视的干扰，因而能在较宽广的共振区间内吸收反应气体的带电粒子。对于该混合共振来说，反应室的压强高达现有技术压强的102-105倍。
图1是本发明化学汽相淀积设备的横剖面视图。
图2（A）是磁场等势表面的横剖面的曲线图。
图2（B）是电场强度曲线图。
图3（A）和3（B）分别为磁场和电场等势表面的曲线图。
图4是本发明另一个实施例的横剖面视图。
参看图1，这是本发明微波增强式化学汽相淀积设备的示意图。图中，该设备包括一其中界定有等离子体发生区间1和辅助区间2且能维持在适当压力的反应室、一微波发生器4、围绕区间1周围取螺线管形式的电磁铁5和5′、一供电给电磁铁5和5′的电源25和一水冷却系统18。等离子体发生区间1的横截面是圆的。在等离子体发生区间1中设有氮铝化之类的高导热陶瓷制成的衬底夹具10′，衬底10即装在夹具10′中。衬底夹具10′系用红外光24照射和加热到150-1000℃，红外光24则由红外加热器20发射，从红外反射抛物面镜21反射回来，再通过透镜22聚焦到夹具10′的背面上。编号23表示红外加热器20的电源。抽真空系统是为将反应室抽成真空而设的，它包括涡轮分子泵8和旋转泵14，两者都通过控制阀11、12和13与反应室相连。衬底温度只能与反应室中所产生的等离子气体一起达到足够的温度值。在这种情况下，可以不用加热器。此外，视乎等离子体的情况而定，衬底的温度可能会高得不适宜进行反应。在这种情况下就要配备冷却装置。本设备的操作过程如下。
将衬底10装到衬底夹具10′上并用红外光24加热到500℃。然后从气体引入系统6以10SCCM（标准状况下每分钟流过的立方厘米）的流率引入氢气，微波发生器通过微波引出窗口15将等于或高于1千高斯（例如2.45千兆赫）的微波发射到承受磁铁5和5′感应出来的约2千高斯磁场的等离子体发生区间1中。微波能在区间1将氢气激发成高密度的等离子体状态。高能电子和氢原子净化衬底表面。除引入氢气外，还通过引入系统7输入C2H2和CH4，并按前述激发氢气的同一个方式在133×102-1.06×105帕下用微波能进行激发。化学汽相反应的结果使碳以金刚石薄膜或i-碳（绝缘碳）的形式淀积下来。i-碳由金刚石与非晶碳的混合物组成。
图2（A）是磁场在图1区域30的分布曲线图。图2（A）的曲线系沿等势表面绘制的，其上标有磁力为2000高斯的磁铁5所感应的磁场强度值。调节磁铁5和5′的磁力就可以控制磁场强度，使得磁场在磁场（875±185高斯）和电场相互作用的区域100中待涂敷的整个表面上基本上均匀分布。图中，编号26表示满足磁场与微波频率之间的ECR（电子回旋共振）条件的875高斯等势表面。当然，根据本发明，由于反应室的压力高（1-800托），因而不能产生ECR，而是在包括BCR情况的等势表面在内的广大区域内产生混合回旋共振（MCR）。图2（B）是对应于图2（A）的曲线图，表示等离子体发生区间1中微波的电场强度。电场强度在区域100′和100′中取最大值。但在区域100′中要加热衬底10′而不干扰微波的传播是有困难的。在其它区域中，薄膜淀积得不均匀，淀积出来的薄膜呈环形。因此将衬底放置在区域100中。等离子体横向流动。根据实验，可以在直径小于100毫米的圆形衬底上形成均匀的薄膜。薄膜最好是在反应室内在直径小于50毫米、厚度和质量均匀的圆形衬底上形成。要涂敷更大的衬底时，微波频率可采用1.225千兆赫以使区间1的直径加倍。图3（A）和3（B）是表示等离子体发生区间1横剖面上磁场和电场分布 情况的曲线图。图中圆圈中绘制的曲线相应于各等势表面。如图3（B）所示，电场达到的最大值是25千伏/米。
我们绘制了根据本发明制造的薄膜的衍射图象。从得出的结果可以看到带有表示有金刚石存在的斑点的晕圈图形。晕圈图形（这对应于非晶态）在衬底温度上升时逐步消失，当温度升到650℃以上时薄膜变成金刚石。低于150℃时，i碳薄膜形成不起来。为对比起见，我们按上述方式但不采用磁场制造薄膜。结果，淀积出石墨薄膜。
以同样的方式，利用甲基硅烷，和铝化合物气体和氨气分别作为反应气体，可以制取多晶碳化硅薄膜和氮化铝薄膜。此外，以类似方式还可以制取钨、钛、钼或它们的硅化合物等其它高熔点薄膜。
参看图4。这是本发明另一个实施例的示意图。图中，该设备包括一其中界定有等离子体发生区间1和辅助区间2且能维持在适当压强的反应室、一微波发生器4、由电源25供电的电磁铁5和5′和一水冷却系统18。等离子体发生区间的横剖面是圆的。在等离子体发生区间1中，具有内弯边缘的空心圆筒10′可转动地支撑在区间中，因而从微波发生器4发射出来的微波沿圆筒轴线通过圆筒。圆筒10′由不锈钢或石英制成，并由电动机16通过一齿轮传动装置使其转动。抽真空系统是为将了反应室抽成真空而设的，它包括涡轮分子泵8和旋转泵14，两者都通过控制阀11、12和13与反应室相连。本设备的操作过程如下：
将待涂敷的物体10，例如金属、塑料、陶瓷部件（象齿轮、螺钉、装饰品模板或碾磨用的微粒等）放入圆筒10′中，并在操作过程中以0.1-10转/分的转速使之转动。以100赫至10千赫的频率使圆筒10′微振（微振装置在图中没有示出）。这一转动和振动过程使暴露在周围环境的物体表面在操作过程中一直在转换。反应室用涡轮分子泵8和旋转泵14抽成1.33×10-4帕或更高的真空度。然后从气体引入系统6以30SCCM的流率将氩、氦或氢气作为非生产性气体引入到反应室中1，再由500 瓦的微波发生器通过微波引入窗口15将2.45千兆赫的微波发射到承受磁铁5和5′感应出来的约2千高斯磁场的等离子体发生区间1中。非生产性气体的压强为1.33×10-2帕。微波能在区间1中产生高密度的等离子体。用高能电子和非生产性原子净化物体10的表面。除引入非生产性气体外，还通过引入系统7引入1.33×102～1.06×105帕，最好是3.99×102帕～3.99×103帕，例如1.33×103帕的C2H2、C2H4和/或CH4，并用微波能以上述用非生产性气体进行激发的方式进行激发。混合共振的结果使碳以金刚石薄膜或i碳薄膜的形式淀积在物体10上。在本实施例中，可以象图1那样采用图1所示的加热装置。
磁场和电场的分布情况与结合前一个实施例说明的图2（A）、2（B）、3（A）和3（B）的情况一样，因此这里不再赘述。
我们绘制了根据本发明制成的薄膜的衍射图象。从得出的结果可以看到带有表示有金刚石存在的斑点的晕圈图形。晕圈图形在衬底温度升高时逐渐消失，当温度超过650℃时，薄膜变为金刚石。低于150℃时，i碳薄膜形成不起来。为对比起见，我们按上述方式但不采用磁场制造薄膜。结果淀积出石墨薄膜。
以同样方式，利用甲基硅烷，和铝化合物气体和氨气分别作为反应气体，可以制取多晶碳化硅薄膜和氮化铝薄膜。此外，以类似方法还可以制取钨、钛、钼或它们的硅化合物等其它高熔点薄膜。举例说，按照本发明可以制取BN或BP薄膜。
反应室的压强选取ECR情况所需用的压强，以便产生初级等离子体放电。在放电持续进行的同时，将压强调到1.33×102至3.99×105帕，在这种场合下产生混合共振，等离子体的粒子平均自由路径为0.05毫米至若干毫米，通常不超出1毫米。
本发明提出的方法适宜制造包括一个或多个稀土元素、一个或多个碱土元素（包括Be和Mg）和Cu的超导电陶瓷。在这种情况下，生产气体 是用氧气在诸元素化合物的溶液中吹泡制备的。例如，Y（OC2H5）3、Ba（OC2H5）和CuBr3的烯属烃或囟化物的有机溶液（苯或醇溶液）或水溶液，使Y、Ba和Cu之间的化学当量比为1∶2∶3。淀积物的化学计算式为YBa2Cu3O6-8。可以用所谓喷涂法代替吹泡法，具体作法是将诸元素的化合物以细粉末的形式与高压氧气吹入反应室中。
本发明不应局限于上述个别实施例，熟悉本专业的人士都可对上述实施例进行多种修改或更改。举例说，可以采用具有多角形横剖面的任何空心构件代替空心圆筒。虽然上述诸实施例只在磁场存在的情况下使用微波能，但也可在远离混合共振的位置往混合共振所激发的反应气体上施加光子能量。

Claims (8)

1、一种等离子体处理方法，包括下列步骤：
将待处理的衬底放在一反应室中；
将一反应气体输进所说反应室；
在所说反应室中建立一磁场；
将微波供给所说反应室，以在所说磁场影响下由所说微波激发所说反应气体；
其特征在于，所说衬底放置在磁场强度为满足电子回旋共振条件的磁场强度的±21.2%之处。
2、根据权利要求1的方法，其特征在于，所说微波频率为2.45千兆赫。
3、根据权利要求2的方法，其特征在于，所说衬底处的所说磁场强度为875±185高斯。
4、根据权利要求1的方法，其特征在于，所说反应气体的压力为1.33×102-1.06×105帕。
5、一种等离子体处理设备，包括：
一个反应室;
一个在所说反应室中感生磁场的装置;
一个将微波供给所说反应室的装置;
一个在所说反应室中装设的衬底支架，用以支持待处理的衬底;
其特征在于，所说支架置放在使所说待处理衬底置于所说磁场强度为满足电子回旋共振条件的磁场的±21.2%之处。
6、根据权利要求5的设备，其特征在于，所说微波的频率为2.45千兆赫。
7、根据权利要求6的设备，其特征在于，所说磁场强度为875±185高斯。
8、一种在衬底上形成碳膜的方法，它包括：
将含碳化合物气体的反应气体输进一反应室;
将具有2.45千兆频率的微波发射到所说反应室;
在所说反应室建立一磁场，使回旋共振产生以激发所说反应气体;以及
在所说衬底上淀积一碳膜;
所特征在于，所说衬底在所说反应室中被置于所说磁场为875±185高斯之处。
CN87107779A 1986-11-10 1987-11-09 加有磁场的微波等离子体化学汽相淀积法 Expired CN1017726B (zh)

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JP62000298A JPH0676665B2 (ja) 1987-01-05 1987-01-05 薄膜形成方法
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KR930005010B1 (ko) 1993-06-11
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