CN107406967B - 氧化铝膜的成膜方法和形成方法以及溅射装置 - Google Patents
氧化铝膜的成膜方法和形成方法以及溅射装置 Download PDFInfo
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- 238000004544 sputter deposition Methods 0.000 title claims abstract description 31
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- 238000000137 annealing Methods 0.000 claims abstract description 27
- 239000004411 aluminium Substances 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 8
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- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
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- 229910052786 argon Inorganic materials 0.000 description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种可形成即便以低温退火处理也能结晶的氧化铝膜的成膜方法和形成方法以及溅射装置。本发明的氧化铝膜的成膜方法包括，在真空室(1)内配置氧化铝制成的靶(2)和待处理基板(W)，向真空室内导入稀有气体，向靶施加高频电力并通过溅射在基板表面形成氧化铝膜，将成膜过程中的真空室内的压力设定在1.6～2.1Pa的范围内。
Description
技术领域
本发明涉及一种氧化铝膜的成膜方法和形成方法以及溅射装置。
背景技术
近年来，作为大容量半导体存储器的3D(三维)-NAND闪存备受关注。3D-NAND闪存是将多层存储单元层叠制成，在其制造工序中，包含形成氧化铝膜的工序或使用形成的氧化铝膜作为硬掩膜的蚀刻工序等。对于这种用途的氧化铝膜的成膜方法，已知的是ALD法(例如参照非专利文献1)，但其存在成膜速度慢的问题。因此人们正在研究使用生产效率好的溅射法形成氧化铝膜。
通常已知的是通过溅射法形成氧化铝膜时，该膜是非晶膜，非晶氧化铝膜耐蚀刻性低，单纯的非晶氧化铝膜无法起到硬掩膜的作用。因此，以往是在蚀刻工序前，通过对非晶氧化铝膜实施退火处理并使氧化铝膜结晶，来提高耐蚀刻性(例如参照专利文献1)。
然而，由于3D-NAND闪存的制造工序数比以往的2D(二维)-NAND闪存多，所以从热经历减少的观点看，优选使氧化铝膜的结晶温度(退火温度)下降到850℃以下，优选800℃以下。
但是，在通过溅射法形成氧化铝膜时，一般是在不对基板积极加热的室温下成膜，一旦降低对在这样的室温下形成的氧化铝膜实施的退火处理的温度，就会出现氧化铝膜不结晶的问题。
现有技术文献
专利文献
【专利文献1】专利公开2003-168679号公报
非专利文献1
【非专利文献1】孙进云，及其他3人，“大面积原子层沉积和使用AlCl3和H2O生成Al2O3的表征”，韩国社会期刊，第33卷，1998年11月，第170～174页(Sun Jin YUN、及其他3人、「Large-Area Atomic Layer Deposition and Characterization of Al2O3film GrownUsing AlCl3and H2O」、Journal of the Korean Society、Vol.33、November 1998、pp.S170-S174)
发明内容
发明要解决的技术问题
本发明的课题是提供一种即便以低温退火处理也能结晶的氧化铝膜的成膜方法和形成方法以及溅射装置。
解决技术问题的手段
为解决上述课题，本发明的氧化铝膜的成膜方法在真空室内配置氧化铝制成的靶和待处理基板，向真空室内导入稀有气体，向靶施加高频电力并通过溅射在基板表面上形成氧化铝膜，所述氧化铝膜的成膜方法，其特征在于：成膜过程中的真空室内的压力设定在1.6～2.1Pa的范围内。
采用本发明，通过在溅射成膜过程中将真空室内的压力设定在1.6～2.1Pa的范围内，即便降低在使用本发明的成膜方法形成非晶氧化铝膜后实施退火处理的温度，也可使氧化铝膜结晶。在下述实验中，确认了即便将退火处理温度设定在800～850℃，也可使氧化铝膜结晶。此外，一旦真空室内压力达不到1.6Pa，则存在耐蚀刻性下降的情况，另一方面，一旦超过2.1Pa，则存在导致生产效率下降或薄膜厚度的基板面内分布恶化的情况。
在本发明中，优选在溅射成膜过程中将基板加热到450～550℃。由此，所形成的非晶氧化铝膜的构成原子与在室温下所形成的氧化铝膜的构成原子相比，实施了退火处理时更容易移动。因此，即便降低在使用本发明的成膜方法形成非晶氧化铝膜后实施的退火处理的温度，也可使氧化铝膜结晶。在下述实验中，确认了即便将退火处理温度设定在800℃，也可使氧化铝膜结晶。
再有，在本发明中，优选将施加在靶上的高频电力设定在1kW～4kW的范围内。一旦超出该范围，则存在生产效率或耐蚀刻性下降的情况。
采用本发明的氧化铝膜的形成方法，可通过使用上述氧化铝膜的成膜方法形成氧化铝膜，以800～850℃对所形成的氧化铝膜进行退火，使氧化铝膜结晶。此时，如果将氧化铝膜形成过程中的基板温度设定在450～550℃的范围内，则可以在800℃下进行退火使氧化铝膜结晶，是有利的。
适用于实施上述氧化铝膜的成膜方法的本发明的溅射装置，具有：设置有氧化铝制成的靶的真空室；在真空室内与靶相对地保持待处理基板的台架；向靶施加高频电力的溅射电源；以及向真空室内导入稀有气体的气体导入装置；所述溅射装置，其特征在于，具有：将成膜过程中的基板的温度加热到450～550℃的范围内的加热装置。
附图说明
图1是说明本发明的实施方式的溅射装置的结构示意图。
图2是确认本发明效果的实验结果的图表。
图3是确认本发明效果的实验结果的图表。
具体实施方式
以下参照附图，以用溅射法在基板W表面上形成氧化铝膜的情况为例，说明本发明的实施方式的氧化铝膜的成膜方法和溅射装置。
参照图1，本实施方式的溅射装置SM具有限定处理室10的真空室1。真空室1的侧壁经排气管11与真空泵P相连，将真空室1内抽真空到规定压力(例如1×10-5Pa)。再有，真空室1的侧壁与来自气源12的气体导入管13相连，可将由质量流量控制器14控制流量的氩气等稀有气体导入真空室1内。这些气源12、气体导入管13和质量流量控制器14构成本发明的“气体导入装置”。以下表示“上”、“下”方向的词语以图1为基准进行说明。
在真空室1的上部设置有阴极单元C。阴极单元C具有靶2、配置在该靶2的上方的磁铁单元3。靶2由氧化铝制成，根据基板W的轮廓以公知的方法形成为平面视图为圆形或矩形。靶2经省略图示的铟或锡等粘接材料与在成膜时冷却靶2的铜制成的背板21接合，在该状态下，靶2的溅射面2a在下方，经绝缘板I安装到真空室1的上部。靶2上连接有作为溅射电源E1的高频电源的输出，在溅射过程中，向靶2例如施加1kW～4kW的13.56MHz的高频电力。磁铁单元3是使溅射面2a的下方空间内产生磁场，捕捉在溅射时在溅射面2a的下方电离的电子等并使从靶2飞散的溅射粒子效率良好地离子化的公知结构的磁铁单元，此处省略对其的详细说明。
在真空室1的下部，设置有将基板W保持在与靶2相对位置上的台架4。在台架4上设置有省略图示的静电卡盘用的电极，通过向该电极施加卡盘电压，可对基板W进行定位。在台架4中内置有例如电阻加热式加热器等的加热装置41，可将成膜过程中基板W的温度加热保持在450℃～550℃的范围内。同时，台架4上形成有用于使冷却水等的冷媒循环的通路42，可冷却保持在台架4上的基板W。
再有，真空室1内设置有不锈钢等金属制成的上下一对的防护板5u、5d，在溅射成膜过程中，可防止溅射粒子附着在真空室1的内壁面上。上述溅射装置SM具有包含公知的微型计算机或定序器等的未进行图示的控制装置，统一控制加热装置41的运行、溅射电源E1的运行、质量流量控制器14的运行、真空泵P的运行等。以下对使用上述溅射装置SM的成膜方法进行说明。
首先，将真空室1内(处理室1a)抽真空到规定的真空度，通过图外的运送机器人将基板W运送到真空室1内，将基板W定位并保持在台架4上。接着，使加热装置41运行并将基板W加热到450℃～550℃。一旦基板W的温度达到规定温度(例如450℃)，则将作为溅射气体的氩气气体以175～250sccm的流量导入真空室1内(此时的压力是1.6～2.1Pa)，通过从溅射电源E1向靶2施加高频电力，在处理室10内形成等离子体气氛。由此，靶2被溅射，由此产生的溅射粒子飞散并附着堆积在基板W表面，形成非晶氧化铝膜。
此处，向靶2施加的高频电力优选例如设定在13.56MHz、1kW～4kW的范围内。一旦超过该范围，则存在生产效率或耐蚀刻性下降的情况。另外，成膜过程中真空腔内的压力不到1.6Pa时，有时耐蚀刻性降低，另一方面，一旦超过2.1Pa，则存在生产效率下降或薄膜厚度的基板面内分布恶化的情况。
采用以上的实施方式，为了在溅射成膜过程中将基板W加热到450℃～550℃，构成所形成的非晶氧化铝膜的原子与构成在室温下所形成的氧化铝膜的原子相比，在实施了退火处理时更容易移动。因此，即便将在使用本实施方式的成膜方法进行成膜后实施的退火处理的温度降低到800℃左右，也可使氧化铝膜结晶。
再有，通过在溅射成膜过程中将真空室内的压力设定在1.6～2.1Pa的范围内，即便将在使用本实施方式的成膜方法进行成膜后实施的退火处理的温度降低到800～850℃，也可使氧化铝膜结晶。
接着，为确认本发明的效果，使用上述溅射装置SM进行接下来的实验。在本实验中，使用Φ300mm的硅晶片作为基板W，在组装有氧化铝制成的靶2的真空室1内的台架4上安装基板W后，使加热装置41运行并将基板W的温度加热到450℃。一旦基板W的温度达到450℃，则以200sccm的流量将氩气气体导入真空室1内(此时真空室1内的压力是1.8Pa)，从溅射电源E1向靶2施加13.56MHz、4kW的高频电力，由此，在处理室10内形成等离子体气氛，在基板W表面形成非晶氧化铝膜。从溅射装置SM中取出形成了该非晶氧化铝膜的基板W，使用灯退火装置(爱发科理工制造“RTA-12000”)以800℃的温度对非晶氧化铝膜实施退火处理，以退火处理后的氧化铝膜为“发明产品1”。通过X射线衍射法分析发明产品1的结果确认了结晶(参照图2)。
再有，除了将成膜过程中的基板W温度设定在250℃这一点外，以与上述发明产品1相同的方法形成非晶氧化铝膜。如图2所示，确认了即便是以800℃对成膜温度是250℃的氧化铝膜实施退火处理也未结晶，以850℃实施退火处理则结晶。同样的，确认了在与成膜过程中不运行加热装置41而将成膜温度设定在25℃(室温)进行成膜时也是一样，即便实施800℃的退火处理也未结晶，而实施850℃的退火处理则结晶。
再有，除去将氩气流量设定为50sccm、175sccm、200sccm(上述发明产品1)、250sccm、300sccm这一点(此时真空室1内的压力是0.2Pa、1.6Pa、1.8Pa、2.1Pa、2.3Pa)外，以与上述发明产品1相同的方法分别形成非晶氧化铝膜。如图3所示，确认了在将氩气流量设定在175sccm、200sccm、250sccm进行成膜时，与上述发明产品1相同，通过800℃的退火处理会结晶。与之相对的，确认了在将氩气流量设定在50sccm、300进行成膜时，实施800℃的退火处理未结晶，实施850℃的退火处理则结晶。由此可知，如果将氩气流量设定在175～250sccm，即成膜过程中的真空室1内压力设定在1.6～2.1Pa的话，可降低退火处理的温度。
再有，除将向靶2施加的高频电力设定在1kW这一点外，以与上述发明产品1相同的方法分别形成非晶氧化铝膜，实施800℃的退火处理进行结晶，以结晶后的产品为发明产品2。并且，以H2O:HF＝500:1的蚀刻液对发明产品1和发明产品2进行湿蚀刻并测量其蚀刻速率。确认发明产品1和发明产品2的蚀刻速率分别为由此，可知一旦将高频电力设定为不到1kW，则蚀刻速率上升，耐蚀刻性下降。
以上对本发明的实施方式进行了说明，但本发明并不受上述内容的限定。例如，如图1所示，台架4与其他的高频电源E2的输出连接，通过在成膜时向台架4施加规定的偏置功率，可使构成氧化铝膜的原子在退火处理时更加地容易移动。此时，作为偏置功率，优选以13～45W施加13.56MHz的高频电力。
附图标记说明
SM…溅射装置、W…基板、1…真空室、2…靶、4…台架、41…加热装置、E1…溅射电源、12，13，14…气体导入装置。
Claims (2)
1.一种氧化铝膜的形成方法，其包括的成膜工序，所述成膜工序在真空室内配置氧化铝制成的靶和待处理基板，向真空室内导入稀有气体，向靶施加高频电力并通过溅射在基板表面上形成氧化铝膜，所述氧化铝膜的成膜方法的特征在于：
在所述成膜工序中，成膜过程中的真空室内的压力设定在 1.6～2.1Pa的范围内，并且在成膜过程中基板温度设定在 450～550℃的范围内，形成非晶氧化铝膜；
还包括退火工序，其对所形成的所述非晶氧化铝膜以800～850℃进行退火使其结晶。
2.根据权利要求 1所述的氧化铝膜的形成方法，其特征在于：
施加在靶上的高频电力设定在 1kW～4kW的范围内。
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