CN1131343A - 制造半导体器件的方法 - Google Patents
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Abstract
用含蒸汽和氧的混合气体首先氧化已形成的绝缘氧化膜，由此造成膜表面上残留易移动的离子的状态。随后为除去残留离子进行热氧化工艺。结果，促进绝缘氧化膜内部的氧化。并改善了绝缘氧化膜表面的绝缘性能。因此能获得有优异耐压特性和很小的或无漏电流的高绝缘电介质膜。
Description
本发明涉及制造半导体器件的方法，特别涉及制造有优异绝缘性能的介质膜的半导体器件的方法。
半导体器件或液晶显示(LCD)装置中，绝缘膜或介质膜用于确保半导体器件或LCD装置中的电路元件之间的电绝缘。而且，绝缘膜或介质膜用于构成半导体存储器件中的存储电容的电介质，或有源矩阵型LCD装置的每个像素中的辅助电容器的介质。这种绝缘膜或介质最好用氧化硅、氮化硅、氧化铝或氧化钽制成。
所来，半导体器件上每单位面积的电路元件的封装密度已增大，LCD装置的图像显示清晰度也明显提高，结果，存储电容器的尺寸，即用作存储电容器的绝缘膜或介质膜的面积已减到最小。这种绝缘膜或介质膜的面积减至最小时，介质膜的静电容量也减小。因而，为了不减小静电容量，必须减小膜厚。或使用有高介电常数的材料作电介质层。然而，随着膜厚减小，膜层耐压(或击穿电压)减小，因而，就可靠性而言对膜厚减小应有某种限制。
而且，具有高介电常数的例如氧化钽膜引起人们注意。然而在用阳极氧化法制成氧化膜时，与氧化硅膜等比较，氧化钽膜常有较大的漏电流和有较差的绝缘性。这是因为氧化钽膜包括电子陷阱或空间电荷极化。在用反应溅射法制成氧化钼膜的情况下由于下氧化物数量增大，使漏电流增大。
为此当将氧化钽膜用于半导体存储器的存储电容器时，功耗增大，当氧化钽膜用于像素的辅助电容器时，或用于有源矩阵型LCD装置的玻璃衬底的保护绝缘膜时，在显示时会出现故障。
为了容易地提高用氧化钽、氧化铝等制成的金属氧化膜的绝缘性，在绝缘氧化膜形成后紧接着对其进行附加的热氧化处理。
该热氧化法通常分为两种，一种热氧化是用包括蒸汽的混合气体在1000℃以下的温度下进行，(以下称作湿退火)。另一种热氧化是用无蒸汽的只有干燥气体进行的(以下称为干退火)。通常，需要热氧化时，可用湿退火或干退火中的任何一种。
然而，按这种常规方法获得的这种绝缘氧化膜的绝缘性不足，而且耐压特性可能也不好。某些情况下，在氧化绝缘膜表面只会出现横向漏电流。
本发明制造半导体器件的方法包括下列工艺步骤：在1000℃以下的温度，用包含蒸汽和氧的混合气体在衬底上形成绝缘氧化膜的氧化步骤；除去残留在绝缘氧化膜上的离子，获得高绝缘的电介质膜。
按本发明的另一方案，制造半导体器件的方法包括以下各工艺步骤：在包含蒸汽和氧的混合气体中，绝缘氧化膜的湿退火步骤；和在退火步骤之后，使绝缘氧化膜上残留的离子还原的离子除去步骤。
本发明一个实施例的湿退火步骤中，使绝缘氧化膜在1000℃以下的温度退火处理。
本发明的另一实施例中，进行湿退火步骤同时升高退火温度。
在本发明的另一实施例中，离子除去步骤包括，在含氧但基本上无蒸汽的气体中对绝缘氧化膜退火的干退火步骤。
本发明的另一实施例中，在湿退火步骤之后，紧接着在湿退火步骤用的同一室内进行干退火步骤。
本发明的另一实施例中，离子除去步骤包括用臭氧等离子体对绝缘氧化膜表面处理的步骤。
本发明的另一实施例中，离子除去步骤包括用氧等离子体对绝缘氧化膜表面处理的步骤。
本发明的另一实施例中，绝缘氧化膜是用溅射法淀积在衬底上的。
按本发明，在1000℃以下的温度，用含蒸汽和氧的混合气体首先氧化绝缘氧化膜。结果，在膜表面上留有易移动的离子。随后，为了除去残留离子，进行热氧化工艺。经过这样处理，促进了绝缘氧化膜内部的氧化，使膜表面的绝缘性能得到改进。
因此，本文所描述的发明提供了制造半导体器件的方法，使半导体器件有高绝缘的优异耐压特性和小的表面漏电流的电介质膜的优点。
本行业的技术人员，在阅读并理解了以下的结合附图所进行的详细说明之后，会更加明了本发明的这些优点和其他优点。
图1是表示按本发明第1和第2实施例对绝缘氧化膜退火时温度分布与气体引入时间的曲线图。
图2是表示用常规的湿退火法对绝缘氧化膜退火时，温度分布与气体引入时间的曲线图。
图3是表示用常规的干退火法对绝缘氧化膜退火时温度分布与气体引入时间的曲线图。
图4是是表示进行第1估算的结构剖面图，并展示了按本发明第1和第2实施例中底涂覆绝缘膜2的表面上的漏电流的测试系统。
图5是第1实施例中第1测试结果曲线图，展示了当图4中所示电极3和5加20伏直流电压时，氧化钽底涂覆绝缘膜2表面上漏电流的曲线。
图6是表示对第1和第2实施例的进行第2估算的液晶面板的剖面图，展示出用液晶材料的电流效应引起的光漫射，对相邻电极间荷电载流子进行静态估算的测试系统。
图7A至7C是第1实包例中第2估算结果曲线图(用氧化钽作底涂覆绝缘膜)，展示出图6中从0至100秒在测试面积内的透射率曲线，图6中电极13与18间加-4伏直流电压时，从0至30秒的透射率曲线，和不加电压时从30秒至100秒的透射率曲线。
图8是第2实施例中第1估算结果曲线图，展示出当图4中电极3和5加20伏直流电压时，氧化铝底涂覆绝缘膜2表面上的漏电流曲线。
图9A至9C是第2实施例中(用氧化铝作底涂覆绝缘膜)第2估算结果曲线图，展示出在图6中测试面积内从0至100秒的透射率曲线，当图6中电极13与18之间加-4伏直流电压时，从0至30秒的透射率曲线，和不加电压从30秒至100秒的传透射率线。
本发明中，首先进行湿退火工艺，使绝缘氧化膜在含蒸汽和氧的混合气体中退火。然后进行离子除去工艺，使绝缘氧化膜中残留的离子数量减少。
湿退火中，绝缘膜中氧化物的扩散速率高于干退火中绝缘膜中氧化物的扩散速率。为此，湿退火可使氧充分地加到绝缘膜内部(深部)，因而绝缘膜中的氧空位可被氧填充。因此，用湿退火可改善绝缘膜自身的绝缘性。然后，湿退火情况下，在绝缘膜表面区同样有残留的易移动的离子如氢氧离子、氢离子等，因而使绝缘膜表面区的绝缘性降低。在已湿退火处理的绝缘膜上淀积其它膜时，这些膜之间的界面处漏电流量增大。另一方面，干退火时，绝缘膜中氧化物的扩散速率较低，因此膜内部供氧不足。这会造成绝缘膜的绝缘性和耐压特性总的损坏。
按本发明由于在湿退火后进行减少绝缘氧化膜中残留的离子数量的离子除去工艺，因而同时改善了氧化膜自身的体绝缘性的其表面区的绝缘性。
以后，将用举例方式结合附图说明本发明。例中，将说明包括半导体器件的LCD装置，如有源矩阵型LCD装置中，淀积在玻璃衬底上底涂覆绝缘膜上排列有许多半导体薄膜晶体管(TET)。为改善LCD的显示质量，底涂覆绝缘膜应有足够的绝缘性，以防止在底涂覆绝缘膜上所形成的电极间电流泄漏。
例1
例1中，氧化钽用作底涂覆绝缘膜。
首先，在玻璃衬底上用溅射法淀积厚度约3000至4000的五氧化钽膜形成底涂覆绝缘膜。对衬底进行本发明图1所示的热处理，更具体地说，将衬底放入退火室内，使温度从室温升至500℃到600℃，温度低于使淀积的氧化钽不会重结晶成多晶态的温度。在温度从150℃升到600℃的时间周期(从图1中圈号1所指示的时间周期)内将包含蒸汽和氧的混合气体引入退火室内。紧接着，给退火室通入干氧，保温1到2小时(图1中圈号2所指的时间周期)，进行本发明的退火工艺。此后，将其上有氧化钽的衬底冷却至室温。
而且，作为对比例，进行湿退火，构成图2所示的另一底涂覆绝缘膜，但退火室内的温度按例1的方式变化。进行干退火，构成图3所示的另一底涂覆绝缘膜。湿退火中，在温度从150℃升到600℃的时间周期内(图2中圈号1所示的时间周期)将包含蒸汽和氧的混合气体引入退火室内，进行退火。另一方面，干退火中，在温度从150℃升到600℃的周期内(图3中圈号2指的时间周期)，干氧引入退火室内，进行退火。
通常可给插在装有沸水的容器中水里的管子通入氧气而生成含蒸汽和氧的混合气体。这种情况下，控制装入容器中供给水的氧气流量和水的温度，来调节含蒸汽和氧的混合气体中蒸汽与氧气的比例，典型的水温设定在以90℃至100℃。然而，产生包含蒸气和氧的混合气体的方法并不限于上述方法。
尽管按10(升/分钟)的流量给退火室供氧来进行干退火，但氧的用量不受此限止，某些情况下，不可避免地会有少量水进入退火室，但这种水(H2O)不会影响除去绝缘氧化膜表面区内残留的离子，干退火中，必须使火室内的气体基本上不含蒸汽(或水)。干退火中，在退火室内即使含有除氧气以外的气体如大气中的氮气，也能充分地除去残留离子，在该例中尽管干退火周期为1至2小时，但1小时以上的时间周期就足够有效地除去易移动的离子。然而在温度低于500℃时进行干退火，则必须连续退火1小时以上，为此，最好在500℃以上进行退火。
正如以上对本发明的例1中2个相应的对比例描述的，在玻璃衬底上形成的本发明的底涂覆绝缘膜包括三种。参见图4，在以标号1表示的玻璃衬底上形成的底涂覆绝缘膜(通常用2表示)。随后，在底涂覆绝缘膜2上顺序形成第1电极3，绝缘膜4和第2电极5，如图4所示。首次估算是测量在电极3和5之间加20伏电压时的漏电流，该测量与底涂覆绝缘膜2与绝缘膜4之间界面的绝缘性能有关，即，与底涂覆绝缘膜2表面区的绝缘特性有关。当该表面区中的漏电流随时间明显增大时，这会引起载流子以电容器电极泄漏，使存储功能或显示质量变坏。这里，电极3和5由钽构成，绝缘膜4由氧化钽膜构成。电极3和5不必用同样材料构成，例如，电极3可用钽构成，电极5可用透明导电材料如ITO等构成。
图5是表示漏电流测试结果曲线图。横座标代表时间T(小时)，纵坐标表示电流I(A/mm2)。图5中曲线(a)表示如图2所示的湿退火的情况，图5中曲线(b)表示如图1所示的本发明的本例情况，图5中曲线(c)表示如图3所示的干退火的情况。
正如从漏电流变化所看到的，按本例处理中的漏电流减小几乎与干退火处理中漏电流减小相同。这表示绝缘膜表面区上不存在易移动的离子，尽管由于引入了含蒸汽和氧的混合气体还会存在其它形式的易移动的离子。
而且，制成图6所示的液晶显示板以进行第2估算，该液晶显示板中，在玻璃衬底1上设置的底涂覆绝缘膜2上形成电极13，两个绝缘膜14和15，和校准膜16。在另一玻璃衬底1上依次构成电极18和校准膜16。使两块玻璃衬底1彼此相对其间设置液晶材料17。第2估算过程如下。用液晶材料的电流效应，给电极13与18之间加-4伏电压，时间为0至30秒，从30秒至100秒不加电压。在那个周期中，静态估算相邻电极13之间的荷电载流子。当底涂覆绝缘膜2的绝缘性能，即估算对象差时，相邻的电极13之间出现漏电流，由此引起相邻电极13之间的透光区内载流子带电，结果使透光区内的液晶材料上产生电压，如图6所示。这引起液晶透射率的改变，用光源和设置在透光区对面的光探测器测量该变化。以这种方式荷电的载流子与液晶反常校准类似，导致显示质量变坏。
图7A至7C是表示估算结果曲线图。每个曲线图中横坐标表示时间T(秒)，在该时间内电极13与18之间加相应的电压，如上所述。纵坐标是透射过透光区的透光率(％)。理想情况下，当电极13与18之间不加电压时，透过透光区的光是100％。
图7A用图2所示湿退火制成的底涂覆绝缘膜2的情况。图7B是用如图1所示本发明的本例制成的底涂覆绝缘膜2的情况。图7C是用图3所示干退火制成的底涂覆绝缘膜2的情况。
用7A和7B的结果表明，在按本发明的图7A所示湿退火条件下和图7B所示的退火条件下透光率没有变。这是因为相邻电极13之间的载流子不带电。这就是说，根据本发明供给膜内部的氧与湿退火情况为相同的量级。
上述第1和第2估算结果表明。按本例，可促进氧供给绝缘氧化膜的内部。此外，能充分除去膜表面上的易移动的离子。
本例中，在氧化钽不会变成多晶态的温度进行湿退火。随后，在同一室内进行离子去除工艺。最好在1000℃以下的温度进行湿退火，以改善绝缘氧化膜的绝缘性能。而且，本发明还有一个附带的优点，就是，在同一退火室内顺序进行湿退火和干退火以便除去离子，而使工艺简化。
例2
例2中氧化铝用于底涂覆绝缘膜。
首先，在玻璃衬底上用溅射法淀积厚度约3000至4000的氧化铝膜，形成涂覆绝缘膜。然后按包括本发明例1所述的退火方式在内的三种方法对各个底绝缘膜退火。此后，对按上述方法退火后的氧化铝进行例1所述的第1和第2估算。
图8展示出按图4所示条件进行的第1估算结果。图9A至9C示出按图6所示条件对液晶板中进行第2估算的结果。图8和9A至9C中，曲线(a)表示如图2中所示的湿退火情况，曲线(b)表示用图1所示退火条件所代表的本发明实例2的情况，曲线(c)表示用图3表示的干退火情况。
从图8和9A至9C发现，在氧化钽的情况下，本发明优于现有技术。
上述例中，退火工艺的最高温度设定为600℃，这个温度是考虑到衬底的玻璃变形点决定的。而且，在600℃以下的温度退火，金属氧化物不会从非晶态变成多晶态。所用衬底的耐热性提高时，经过附加的处理可使结晶温度提高。因而可使衬底在更高温度下加热。然而，最好在1000℃以下进行退火工艺。在1000℃以下退火可减少升温和降温所需的时间，这是提高生产率的关键。此外，降低制造工艺中的能耗可使生产成本降低。
上述例中，使用引入氧气的方法作为除去残留离子的方法，但不能采用紫外臭氧处理或氧等离子处理这种方法，考虑到发明器件的成本增大，操作和处理工艺的复杂性时，采用上述实例中用的简单退火作为基础工艺的方法有更多的优点。
上述实例中，液晶显示装置的玻璃衬底上设置的薄膜晶体管中，说明了在玻璃衬底上设置的底涂覆绝缘膜的情况。然而，本发明不限于这些实例，而可适用所有在衬底上所形成绝缘膜要求高绝缘性衬底的情况。
采用溅射法作为淀积绝缘氧化膜的方法，但本发明不受此限制，本发明也适用于改善用其它方法如等离子CVD法等所淀积的绝缘氧化膜的绝缘性能。
如上面的详细描述，按本发明，在形成绝缘氧化膜后作为其后序处理是连续地在1000℃以下的温度用包含蒸汽和氧的混合气体的氧化工艺和去除残留离子的工艺。因而，可用比较简单的方法获得优异绝缘性能的绝缘氧化膜，其表面上无易移动的离子，其内部空隙被氧充分填充。因此，按本发明，用更简化的工艺，容易地同时改善了有绝缘氧化膜的半导体器件和有半导体器件的液晶显示装置的质量和生产合格率。
在不脱离本发明的思想和范围内本行业的技术人员会容易地做出各种其它改型。因而本发明要求保护的范围不限于上述内容，而且有广义的要求。
Claims (9)
1.一种制造半导体器件的方法，包括以下步骤：
在1000℃以下的温度用包含蒸汽和氧的混合气体来氧化衬底上所形成的绝缘氧化膜；
除去残留在绝缘氧化膜上的离子，以获得高绝缘的介质膜。
2.一种制造半导体器件的方法，包括下列工艺步骤：
形成绝缘氧化膜；
在含蒸汽和氧的混合气体中对绝缘氧化膜退火的湿退火步骤；和
退火步骤后减少绝缘氧化膜上残留离子数量的除去离子的步骤。
3.按权利要求2的方法，其特征是，进行湿退火步骤中绝缘氧化膜在1000℃以下退火。
4.按权利要求3的方法，其特征是，进行湿退火而同时升高退火温度。
5.按权利要求2的方法，其特征是，离子除去步骤包括在含氧但基本不包蒸汽的气体中对绝缘氧化膜退火的干退火步骤。
6.按权利要求5的方法，其特征是，用湿退火步骤的同一退火室进行干退火步骤，并在湿退火步骤之后立即进行。
7.按权利要求2的方法，其特征是，离子除去包括用臭氧对绝缘氧化膜表面处理的步骤。
8.按权利要求2的方法，其特征是，离子除去步骤包括用氧等离子体处理绝缘氧化膜表面的步骤。
9.按权利要求2的方法，其特征是，用溅射法在衬底上淀积绝缘氧化膜。
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| JP6320786A JPH08181135A (ja) | 1994-12-22 | 1994-12-22 | 半導体装置の製造方法 |
| JP320786/94 | 1994-12-22 |
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| CN1131343A true CN1131343A (zh) | 1996-09-18 |
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| USD981973S1 (en) | 2021-05-11 | 2023-03-28 | Asm Ip Holding B.V. | Reactor wall for substrate processing apparatus |
| USD980813S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas flow control plate for substrate processing apparatus |
| USD980814S1 (en) | 2021-05-11 | 2023-03-14 | Asm Ip Holding B.V. | Gas distributor for substrate processing apparatus |
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-
1994
- 1994-12-22 JP JP6320786A patent/JPH08181135A/ja not_active Withdrawn
-
1995
- 1995-12-21 KR KR1019950072368A patent/KR960026379A/ko not_active Application Discontinuation
- 1995-12-22 CN CN95110000A patent/CN1131343A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08181135A (ja) | 1996-07-12 |
| KR960026379A (ko) | 1996-07-22 |
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