CN109306469A - 通过使用负偏压的peald沉积膜的方法 - Google Patents

通过使用负偏压的peald沉积膜的方法 Download PDF

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CN109306469A
CN109306469A CN201810671234.7A CN201810671234A CN109306469A CN 109306469 A CN109306469 A CN 109306469A CN 201810671234 A CN201810671234 A CN 201810671234A CN 109306469 A CN109306469 A CN 109306469A
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film
bias voltage
electrode
method described
plasma
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铃木俊哉
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ASM Japan KK
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Abstract

一种通过PEALD在衬底上形成膜的方法包含沉积循环，每个沉积循环包含：(i)以脉冲形式将前体馈送到反应空间以使前体吸附在衬底的表面上；(ii)在步骤(i)之后，将RF功率施加于第二电极以在所述反应空间中产生等离子体，前体吸附的所述表面暴露于所述等离子体，由此在所述表面上形成子层；以及(iii)在步骤(ii)中施加RF功率时将偏置电压施加于所述第二电极，参考第一电极的表面上的电位，所述偏置电压为负，其中所述循环重复以沉积多个子层，直到由所述子层构成的膜具有所要厚度。

Description

通过使用负偏压的PEALD沉积膜的方法
技术领域
本发明大体上涉及通过使用由负偏置电压改良的电容耦合等离子体(CCP)的等离子体增强原子层沉积(PEALD)在衬底上形成膜的方法。
背景技术
通过等离子体增强原子层沉积(PEALD)而沉积的电介质膜广泛用在半导体制造业中，因为在沉积于纵横比约为10的沟槽中时，此类膜的保形性极高，例如100％。然而，使用电容耦合等离子体(CCP)的常规PEALD具有以下问题。等离子体是含有正离子和自由电子的离子化气体，所述正离子和自由电子的比例或多或少不产生总电荷，且在使用CCP的PEALD中，使用离子和基团完成膜的形成。离子轰击对于膜生长和膜质量较重要。然而，施加在衬底表面上的强烈离子轰击会产生问题。即，在许多PEALD工艺中，离子轰击会恶化膜特性。图5示出膜沉积中因强烈离子轰击45所致的问题，其中(a)示出沉积膜42与衬底41之间的结合破坏，(b)示出沿着沉积膜42与衬底41之间的界面形成浮泡43a(浮泡43b还形成于沉积膜表面上)，且(c)示出沉积膜42与衬底41之间沉积的底层44的损坏或蚀刻。
有可能通过减小等离子体功率和/或增大过程压力来缓解强烈离子轰击的不利影响。然而，当等离子体功率减小时，等离子体密度会减小，从而产生不均匀或不一致的等离子体分布，且当过程压力增大时，等离子体的激发变得困难和不稳定。
鉴于上述问题，本发明人完成本发明，本发明的至少一些实施例可有效解决上述问题中的一些或全部。
对与现有技术相关的包含上文所论述的那些问题和解决方案的任何论述仅仅出于提供本发明上下文的目的而包含在本公开中，且不应视作承认在进行本发明时已知晓任何或全部所述论述。
发明内容
一些实施例提供一种在由面向彼此的电容耦合的第一和第二电极限定的反应空间中通过等离子体增强原子层沉积(PEALD)在衬底上形成膜的方法，其中衬底面向第二电极放置在第一电极上，所述PEALD包括沉积循环，每个循环包括：(i)以脉冲形式将前体馈送到反应空间以使前体吸附于衬底的表面上；(ii)在步骤(i)之后，将RF功率施加于第二电极以在反应空间中产生等离子体，前体吸附的表面暴露于所述等离子体，由此在所述表面上形成子层；以及(iii)在步骤(ii)中施加RF功率时将偏置电压施加于第二电极，参考第一电极表面上的电位，所述偏置电压为负，其中重复所述循环以沉积多个子层，直到由所述子层构成的膜具有所要厚度。可在最小修改的情况下使用包含任何常规设备的任何合适的CCP型PEALD设备实施上述方法，以便产生具有低离子能量的高密度等离子体。一些实施例的特征可在于以下特征：(1)具有较低等离子体电位的较低离子能量过程；(2)具有较高等离子体密度的较高产出量；以及(3)上部电极上较少的粒子产生。放置衬底的下部区处的离子能量控制能力尤其显著。如上文相对于图5所论述，离子轰击可引发层间分离、起泡或蚀刻以及PEALD膜特性恶化等缺陷；但一些实施例可有效地消除这些问题且尤其有利于离子轰击敏感的PEALD工艺，从而实现具有良好膜特性的膜形成。
出于概述本发明的方面和所实现的优于相关技术的优势的目的，本发明的某些目标和优势描述于本公开中。当然，应理解，未必所有此类目标或优势都可根据本发明的任一特定实施例实现。因此，举例来说，所属领域的技术人员将认识到，本发明可按实现或优化如本文中教示的一个优势或一组优势的方式实施或实现，而不必实现如本文中可能教示或表明的其它目标或优势。
本发明的其它方面、特征和优势将根据下文的详细描述而变得显而易见。
附图说明
现将参考优选实施例的图来描述本发明的这些和其它特征，所述优选实施例在于说明而非限制本发明。各图出于说明性目的被大大简化并且未必按比例。
图1是根据本发明的实施例的用于使用伴有负偏置电压的单频RF功率沉积电介质膜的PEALD(等离子体增强原子层沉积)设备的示意性表示。
图2是根据本发明的实施例的用于使用伴有负偏置电压的双频RF功率沉积电介质膜的PEALD(等离子体增强原子层沉积)设备的示意性表示。
图3是根据本发明的实施例的用于测量包含在构成电位的分量中的直流电分量以确定偏置电压的电路的示意性表示。
图4示出使用在本发明的实施例中可用的流通系统(FPS)的前体供应系统的示意性表示，其中(a)示出带有前体的气流以及(b)示出不带前体的气流。
图5示出由强烈离子轰击引起的膜沉积中的问题，其中(a)示出沉积膜与衬底之间的结合破坏，(b)示出沿着沉积膜与衬底之间的界面形成浮泡，以及(c)示出沉积膜与衬底之间沉积的底层的损坏或蚀刻。
图6示出实施例，其中在(a)中DC偏置电压随着工艺循环的进行而改变，即，在(b)中离子能量随着工艺循环的进行而改变。
图7示出实施例，其中(a)示出负DC偏置电压施加于上部电极(“w/DC偏压”)时和没有施加负DC偏置电压(“w/o DC偏压”)时电极之间的电位特征曲线，且(b)是电极之间的等离子体分布的示意性表示。应注意，为易于说明，已将定向逆时针旋转90度。
图8示出根据本发明的实施例的示意性工艺工序，其中步升线表示接通状态或增大量状态，而步降线表示断开状态或减小量状态，且每个区段的高度和持续时间未必按比例。
图9是示出根据本发明的实施例的负偏置电压的量与底层有机膜的损坏之间以及负偏置电压的量与沉积在有机膜上的SiCNO膜的湿法蚀刻速率之间极大地简化的关系的图。
具体实施方式
在本公开中，取决于上下文，“气体”可包含汽化固体和/或液体，且可由单一气体或气体混合物构成。同样，取决于上下文，冠词“一”是指一种物种或包含多个物种的属。在本公开中，通过喷头引入到反应室的用于沉积的工艺气体可包括含硅前体和添加气体、主要由含硅前体和添加气体组成或构成。所述添加气体可包含用于氧化、氮化和/或碳化前体的反应气体和在RF功率施加于添加气体时用于激发前体的惰性气体(例如，稀有气体)。惰性气体可作为运载气体和/或稀释气体馈送到反应室。此外，在一些实施例中，不使用反应气体，且仅使用稀有气体(作为运载气体和/或稀释气体)。前体和添加气体可作为混合气体或单独地引入到反应空间。可利用稀有气体等运载气体引入前体。除工艺气体外的气体，即，在不穿过喷头的情况下引入的气体，可用于例如密封反应空间，这包含稀有气体等密封气体。在一些实施例中，术语“前体”大体上是指参与产生另一化合物的化学反应的化合物，且尤其是指构成膜基质或膜的主构架的化合物，而术语“反应物”是指并非前体的与前体相关联而使用且激活前体、使前体改性或催化前体的反应的化合物，其中在施加RF功率时，所述反应物可提供元素(例如O、N和/或C)到膜基质且变成膜基质的一部分。术语“惰性气体”是指在未施加RF功率(或其它电磁能)时不活泼、但在施加RF功率(或其它电磁能)时可变成等离子体态以激发前体或改造膜的气体，但不同于反应物，其可能不会变成膜基质的一部分或并入其中。
在一些实施例中，“膜”是指在垂直于厚度方向的方向上连续延伸的基本上无小孔的覆盖整个目标或相关表面的层，或仅仅是指覆盖目标或相关表面的层。在一些实施例中，“层”是指形成于表面上的具有某一厚度的结构，或膜或非膜结构的同义词。膜或层可由具有某些特性的离散单膜或单层构成或由多个膜或层构成，且邻近膜或层之间的边界可以透明或可以不透明，且可基于物理、化学和/或任何其它特性、形成过程或工序和/或邻近膜或层的功能或目的而建立。此外，在本公开中，由于可工作范围可基于常规工作而确定，因此变量的任何两个数字可构成变量的可工作范围，且所指示的任何范围可包含或排除端点。另外，所指示的变量的任何值(不论它们是否用“约”指示)可指精确值或近似值且包含等同物，且在一些实施例中可指平均值、中值、代表值、大部分值等。此外，在本公开中，在一些实施例中，术语“由…构成”和“具有”独立地指“典型地或广泛地包括”、“包括”、“基本上由…组成”或“由…组成”。在本公开中，在一些实施例中，任何限定的含义未必排除普通和惯用含义。
在本公开中，在未指定条件和/或结构之处，鉴于本公开，所属领域的技术人员可容易地按照常规实验提供此类条件和/或结构。
在所有的公开实施例中，实施例中所用的任何要素可出于既定目的而利用与其同等的任何要素替换，包含本文中明确、必须或本质上公开的那些要素。此外，本发明可同等地适用于设备和方法。
将参照优选实施例来阐述实施例。然而，本发明不限于所述优选实施例。
如上文所论述，在一些实施例中，在由面向彼此的电容耦合的第一和第二电极限定的反应空间中通过等离子体增强原子层沉积(PEALD)在衬底上形成膜、其中衬底面向第二电极放置在第一电极上的方法中，所述PEALD包括沉积循环，每个循环包括：(i)以脉冲形式将前体馈送到反应空间以使前体吸附于衬底的表面上；(ii)在步骤(i)之后，将RF功率施加于第二电极以在反应空间中产生等离子体，前体吸附的表面暴露于所述等离子体，由此在所述表面上形成子层；以及(iii)在步骤(ii)中施加RF功率时将偏置电压施加于第二电极，参考第一电极表面上的电位，所述偏置电压为负，其中重复所述循环以沉积多个子层，直到由所述子层构成的膜具有所要厚度。
在一些实施例中，所述偏置电压是DC电压。在一些实施例中，所述偏置电压是具有1MHz或更低的频率的AC电压，其平均电压不为零。通常，所述偏置电压是DC电压，但只要离子可遵循电流的改变，那么偏置电压可为AC电压或RF功率，例如具有1MHz或更低频率的RF功率。
在一些实施例中，第一电极接地，其中RF功率以及偏置电压仅施加于第二电极。在一些实施例中，具有不同频率的RF功率分别施加于第一和第二电极，且偏置电压仅施加于第二电极。
在一些实施例中，在步骤(ii)中，等离子体是氢等离子体。在一些实施例中，在步骤(ii)中，等离子体是选自以下组成的组的一种或多种气体的等离子体：H2、N2、O2、NH3、NxHy(x和y是整数)、N2O、NO2、CO2和稀有气体，以及前述任一种的混合物。在一些实施例中，在步骤(ii)中，由于不论气体类型均可通过使用负偏压电压实现减小等离子体电位的效果，即，减小离子能量，因此所述等离子体是任何合适气体的等离子体。
在一些实施例中，偏置电压的平均值大于0V(例如10V或更大)但不超过1,000V，其中以偏置电压在参考第一电极表面上的电位时为负的方式施加所述偏置电压(在本公开中，所述偏置电压表达为绝对值，且术语“负”是指用以减小第一电极与第二电极之间的电位的施加方向，除非另外说明)。由于用于PEALD的工艺条件(例如50到1,000W的RF功率(13.56MHz)、30到3,000Pa的压力)会变化，因此可基于在选定工艺条件(例如使用HF溶液的湿法蚀刻速率)下沉积的膜的质量和/或通过层的横截面的TEM图像评估的底层(例如有机膜)损坏程度来相应地调整偏置电压的平均值。为了减小底层(例如有机膜)的损坏程度，可使用高偏置电压，而为了提高沉积膜的质量，可使用低偏置电压(这包含例如3,000Pa压力等高压条件下的零电压)。图9是示意性地表示上述关系的图，其示出根据本发明的实施例的负偏置电压量与底层有机膜的损坏之间以及负偏置电压量与沉积在所述有机膜上的SiCNO膜的湿法蚀刻速率之间极大地简化的关系。鉴于上述关系，在一些实施例中，平均偏置电压处于10到500V的范围，通常为10到300V。在本公开中，膜的特性包含但不限于抗湿法蚀刻性，这可通过将膜浸没于具有通常为1/100到1/200的稀释率的DHF(经过稀释的氟化氢)溶液中(在一些实施例中，使用HF 0.05-5％的蚀刻溶液，在10到50℃(优选15到30℃)的蚀刻溶液温度下持续1秒到5分钟(优选1到3分钟)的蚀刻)在0.1到5nm/分钟(优选0.5到2nm/分钟)的蚀刻速率下进行评估。
在一些实施例中，在目标膜为离子轰击敏感型时，例如氧化物膜、氮化物膜或碳膜，和/或在目标膜所直接沉积在的底层膜是聚合物膜或非晶硅膜时，偏置电压的使用尤其有效。
在一些实施例中，在步骤(iii)中，偏置电压在循环重复时逐渐减小。在本公开中，术语“逐渐增大(或减小)”是指根据实施例取决于沉积膜、底层、沉积工艺等连续地增大(或减小)、以某一(可确定)速率增大(或减小)、在使用数据点获取回归方程时的连续增大(或减小)、或如同沿着曲线或近似直线绘制数据点一般增大(或减小)、或在平滑数据时连续地增大(或减小)。图6示出实施例，其中在(a)中DC偏置电压随着工艺循环的进行而改变，即，在(b)中离子能量随着工艺循环的进行而改变。如图6所示，当在聚合物膜等某种膜上沉积膜时，离子能量一开始可如(b)中所示较低(即，偏置电压一开始可如(a)中所示较高)以便在开始时抑制聚合物蚀刻，在开始时由于沉积膜仍然较薄，因此底层尤其易受离子轰击影响。随后，由于离子轰击的影响随着工艺循环重复而减轻，因此可减小偏置电压以便提高沉积膜的质量。如(a)中所示，通过在开始处供应偏置电压且接着逐渐将其减小，有可能最小化对底层的损坏，同时提高沉积膜的质量。
在一些实施例中，如图6所示，所述沉积循环实施为第一沉积循环((a)中的步骤“a”)，且PEALD另外包括第二沉积循环((a)中的步骤“c”)，每个第二沉积循环包括步骤(i)和(ii)，且在第一沉积循环之后不再有通过(a)中的中间或过渡步骤“b”实施的步骤(iii)(或基本上没有步骤(iii)，即，偏置电压基本上或几乎为零)。在一些实施例中，中间沉积循环包括步骤(i)到(iii)，其中偏置电压在循环重复时逐渐减小(例如每循环约-1到-20V，通常每循环约-10V)，其中在第一沉积循环之后连续地实施中间沉积循环，且在中间沉积循环之后连续地实施第二沉积循环。在本公开中，取决于实施例，“连续地”是指不中断真空、不作为时间线中断、无任何材料介入步骤、不改变处理条件、紧接其后、作为下一步骤、或在两个结构之间未介入除所述两个结构外的离散物理或化学结构。在一些实施例中，第一沉积循环在膜的厚度达到10nm或更少(例如5nm或更少、3nm或更少、至少1nm、2nm或更多)时终止。当图6中所示的工序应用于在碳膜上使用SiO膜的双重图案化工艺时，步骤“a”由约30个循环构成(以形成具有约2nm的厚度的保护膜)，步骤“b”由约30个循环构成(以通过将离子能量增大到底层碳膜不受损的程度来连续地形成具有约2nm的厚度的SiO膜)，且步骤“c”由约240个循环构成(以在针对膜沉积优化的条件下连续地形成具有约16nm的厚度的SiO膜)。
在一些实施例中，反应气体和运载/稀释气体在整个步骤(i)到(iii)中被连续馈送到反应空间。在一些实施例中，循环另外包括在每个步骤(i)和每个步骤(ii)之后的净化。图8示出根据本发明的实施例的示意性工艺工序，其中步升线表示接通状态或增大量状态，而步降线表示断开状态或减小量状态，且每个区段的高度和持续时间未必按比例。在此工艺工序中，在容纳Si晶片的CCP型反应室中实施沉积工艺。步骤“馈送”、“净化1”、“RF”和“净化2”构成PEALD的一个循环。在“馈送”中，以脉冲形式将前体(例如烷氨基硅烷)馈送到反应室以使前体以化学方式吸附于晶片的表面上，同时连续地馈送反应气体(例如O2)和稀释/运载气体(例如Ar)通过“馈送”、“净化1”、“RF”和“净化2”。在“RF”中，将RF功率施加于反应室以使前体吸附的晶片暴露于反应气体的等离子体，以便在晶片的表面上形成单层。“净化1”和“净化2”是用以从衬底移除不反应成分和副产品的净化步骤，其中反应气体和稀释/运载气体的连续流充当净化气体。在此实施例中，DC偏置电压完全施加于上部电极，而RF功率在“RF”中施加，即，RF功率的“接通”定时和DC偏置电压的“接通”定时完全或基本上同步，使得等离子体中的离子能量在“RF”的整个周期中可受控制。在本公开中，取决于实施例，“基本上相同”、“基本上一致”等等可指无关紧要的差别或所属领域的技术人员认可的差别，例如小于10％、小于5％、小于1％或其任何范围的差别。此外，术语“基本上同步”包含控制电路中不可避免的响应或时间延迟。或者，可在离子能量并不高时在RF功率的脉冲周期期间以脉冲或以更短脉冲施加DC偏置电压。重复一个循环，直到在晶片上获得具有所要厚度的膜。
在一些实施例中，在下文的表1中所示的条件下实施PEALD循环。
表1(数值为近似值)
在施加RF功率时，将偏置电压作为参考第一电极表面上的电位的负电压施加于第二电极。
上文所指示的用于300mm晶片的RF功率可转换成W/cm2(每单位面积晶片的瓦数)，其可应用于具有200mm或450mm等不同直径的晶片。
通常，电介质膜的厚度处于约50nm到约500nm的范围(可根据膜的应用和目的等选择认为合适的所要膜厚度)。电介质膜可用于双重图案化。
上述工艺可用于各种应用中，包含间隔物限定的双重图案化(SDDP)，其中根据本公开实施例或其等同物中的任一个的氧化硅膜可用作竖直间隔物。
在一些实施例中，衬底具有凹槽图案，每个凹槽限定于邻近竖直间隔物之间且由底部和侧壁构成，被称为“沟槽”。即，沟槽是包含由竖直间隔物形成的图案的任何凹槽图案，且其在一些实施例中具有约10nm到约100nm(通常约14nm到约30nm)的宽度(其中当沟槽具有基本上与宽度相同的长度时，其被称作孔/通孔，且其直径是约10nm到约100nm)、约30nm到约100nm(通常约40nm到约60nm)的深度以及约2到约20(通常约2到约5)的纵横比。沟槽的适当尺寸可取决于工艺条件、膜组成、既定应用等而变化。
在一些实施例中，以凹槽图案沉积的膜具有80％到100％、通常大约90％或更高的保形性(沉积在侧壁上的膜厚度与沉积在顶部表面或底部表面上的膜厚度的比率)。
举例来说，工艺循环可使用任何合适的设备执行，包括图1中所示的设备。图1是根据本发明的实施例的用于使用伴有负偏置电压的单频RF功率沉积电介质膜的PEALD(等离子体增强原子层沉积)设备的示意性表示，其合乎需要地结合了被编程以实施下述工序的控制件。
在此图中，通过在反应室3的内部11(反应区)中提供并联且面向彼此的一对导电平板电极4、2，将HRF功率(例如2到100MHz，包含13.56MHz、27MHz、60MHz、100MHz以及前述任何两个数值之间的任何值)20施加于一侧，且使另一侧12电接地，在电极之间激发等离子体。在低一级或基座2(下部电极)中提供温度调节器，且放置其上的衬底1的温度在给定温度处保持恒定。上部电极4也充当喷淋板，且反应气体和/或稀释气体，如果存在的话，以及前体气体分别通过气体线21和气体线22引入到反应室3中，并且通过喷淋板4。另外，在反应室3中，提供具有排气线7的环形管13，反应室3的内部11中的气体通过所述排气线被排出。另外，安置在反应室3下方的传输室5具有密封气体线24以将密封气体通过传输室5的内部16(传输区)引入反应室3的内部11中，其中提供用于分隔反应区和传输区的隔离板14(此图省略闸阀，晶片通过闸阀传入传输室5中或从中传出来)。传输室还具有排气线6。在一些实施例中，在同一反应空间中执行多元素膜的沉积和沉积后处理，使得可在不将衬底暴露于空气或其它含氧气氛的情况下连续实施所有步骤。
在此设备中，通过隔直流电容器(RF截止滤波器或低路径滤波器)32将负偏置电压从DC电源31施加到喷淋板4。使用控制单元34使施加RF功率的定时和施加偏置电压的定时基本上同步，所述控制单元控制安置在RF功率源20、电源20、隔直流电容器32和DC电源31的输出侧上的匹配盒30。控制单元34从测量电极之间的电位的电极电位测量单元33接收信号，使得控制单元可根据所述电极电位控制上述部件。可使用DC电压表测量将要施加于上部电极的偏置电压的值。图3是根据本发明的实施例的用于测量电位的直流电分量以确定偏置电压的电路的示意性表示。DC电压表27放置在扼流圈28(低路径滤波器32)之后，使得仅电位的DC分量可被获取且通过DC电压表27。
以上配置可应用于双频RF功率系统。图2是根据本发明的实施例的用于使用伴有负偏置电压的双频RF功率沉积电介质膜的PEALD(等离子体增强原子层沉积)设备的示意性表示。在此设备中，第二RF功率源36通过匹配盒37连接到下部电极2，且控制单元35控制匹配盒37和第二RF功率源36以及上文所描述的部件。
图7(逆时针旋转90°定向)示出实施例，其中(a)示出负DC偏置电压施加于上部电极(“w/DC偏压”)时和没有施加负DC偏置电压(“w/oDC偏压”)时电极之间的电位特征曲线，且(b)是电极之间的等离子体分布的示意性表示。总的来说，因为等离子体的电子温度高于离子的电子温度，所以参考等离子体电位，壁电位通常因轻且快速移动的电子而为负。换句话说，参考壁电位，等离子体电位通常为正。在本公开中，参考下部电极2的壁电位，即，下部电极2的壁电位被视为零，确定电压的值。在壁表面上，产生离子鞘，这是使电子速度减慢或反射电子且增大离子速度的空间电荷层，其中存在过量的离子，使得等离子体整体保持电中性。如图7的(a)中所示，当没有DC偏置电压施加于上部电极4(“w/o DC偏压”)而RF功率施加于上部电极4时，上部电极4的壁电位是V0dc，其参考下部电极2的壁电位(零)为负，且等离子体电位除了邻近上部和下部电极的壁的区之外为正(等离子体电位使用最大值线和最小值线表达)。当DC偏置电压施加于上部电极4(“w/DC偏压”)而RF功率施加于上部电极4时，上部电极4的壁电位是Vdc，其参考下部电极2的壁电位(零)为负，且等离子体电位除了邻近上部和下部电极的壁的区之外为正(等离子体电位在上部离子鞘中用最大值线和最小值线表达，但在其余区中通过一个线表示，因为最大值与最小值之间的差较小且可简化且接近一个线)。Vdc是V0dc和偏置电压的值ΔVdc(＝V1dc)的总和。通过施加如图7的(a)中所示的偏置电压，上部离子鞘的厚度变得更厚，而下部离子鞘的厚度变得更薄。因此，如图7的(b)中所示，在形成于反应室3的内部11中的上部离子鞘53中，壁表面暴露于离子45的强烈离子轰击(高离子能量)，这引发二次电子51的增加，从而产生较高等离子体密度。另一方面，在形成于等离子体52的靠近下部电极2的另一侧上的下部离子鞘54中，下部离子鞘54的厚度变薄，且壁表面上的衬底1暴露于较少的由离子引起的离子轰击。
由于偏置电压的施加，对底层的损坏或蚀刻可因下部离子鞘54具有低的离子能量(较少离子轰击)而得到有效抑制或减小。另一方面，由于上部离子鞘53具有因强烈离子轰击而释放的二次电子所引发的高等离子体密度，且高等离子体密度状态可通过等离子体52维持，且其可增大下部离子鞘54中的等离子体密度，从而产生较高产出量。在下部离子鞘54中，尽管衬底表面暴露于较少离子轰击，但离子密度因高等离子体密度(高离子剂量)而较高，且因此，RF功率的持续时间可缩短，从而产生较高产出量。此外，由于上部电极4的表面暴露于强烈的离子轰击，因此表面上的膜生长被抑制，从而导致较少粒子产生。此外，由于上部离子鞘53中释放的二次电子增加，且从中产生的等离子体物种分散在整个上部离子鞘53中，因此等离子体均一性可得到显著提高。
在一些实施例中，由于上部电极的表面暴露于强烈的离子轰击，因此可因强烈离子轰击而通过溅射从表面产生金属污染物，从而导致形成于衬底上的膜的金属污染增加。这种趋势随着偏置电压的增加而体现得更多。因此，在一些实施例中，上部电极的表面提前覆盖有作为预涂层的膜，其为与将要形成于衬底上的膜相同的膜。
进一步参考以下工作实例来阐述本发明。然而，所述实例并不在于限制本发明。在未指定条件和/或结构的实例，鉴于本公开，所属领域的技术人员可容易地按照常规实验提供此类条件和/或结构。同样，在一些实施例中，可将具体实例中应用的数值修改至少±50％的范围，并且所述数值是近似值。
实例
实例1(预示的)
在具有有机膜(聚酰亚胺膜)的Si衬底(具有300mm的直径和0.7mm的厚度)上，通过使用图1、3和4中所示的设备的PEALD使用图8中所示的工序在使用氨基硅烷((3-氨丙基)三甲氧基硅烷，APTMS)作为前体、H2作为反应物(H2等离子体)且Ar作为运载气体的条件下沉积具有约30nm的厚度的SiOCN膜，其中用于前体的瓶的温度设置为室温，H2气体流动速率约为100sccm，且Ar气体流动速率约为600sccm，且压力约为4托，且衬底温度约为200℃。施加于上部电极的RF功率(13.56MHz的频率)约为200W。
分别使用0V、-50V、-100V、-200V和-300V的电压在实例中过度RF功率来将偏置电压施加于上部电极。在完成膜沉积之后，评估所得SiOCN膜的质量和底层聚酰亚胺膜的损坏程度以便确定通过偏置电压实现的总体提高。通过使用DHF的湿法蚀刻速率来评估SiOCN膜的质量，且基于膜的横截面的TEM(透射电子显微法)图像来评估聚酰亚胺膜的损坏程度。通过绘制每个评估点，可获得图9中所示的关系等，且因此可确定最优条件。
实例2(预示的)
使用APTMS作为前体、H2作为反应物(H2等离子体)以及Ar作为运载气体以与实例1中的方式类似的方式在形成于300mm Si晶片上的聚酰亚胺膜上沉积具有约30nm的厚度的SiOCN膜，不同之处在于，偏置电压如图6中所示改变。即，在步骤“a”中，使用实例1中确定的其中有机膜的损坏程度极小的偏置电压来重复沉积循环，直到SiOCN膜的厚度达到约3nm，且接着在步骤“b”中，使用在负方向上逐渐增大(例如约-10V/循环)到实例1中确定的其中SiOCN膜的质量为最大值(最优)的偏置电压的偏置电压来连续重复沉积循环，直到SiOCN膜的厚度达到约5nm(增加约2nm)，且接着在步骤“c”中，使用实例1中确定的其中SiOCN膜的质量为最大值(最优)的偏置电压(包含零)来连续重复沉积循环，直到SiOCN膜的厚度达到所要值。因此，成功地沉积高质量SiOCN膜，同时使底层有机膜的损坏最小化。
所属领域的技术人员应理解，可以在不脱离本发明的精神的情况下进行许多各种修改。因此，应明确理解，本发明的形式仅是说明性的，且并不在于限制本发明的范围。

Claims (15)

1.一种在由面向彼此的电容耦合的第一和第二电极限定的反应空间中通过等离子体增强原子层沉积(PEALD)在衬底上形成膜的方法，其中所述衬底面向所述第二电极放置在所述第一电极上，所述PEALD包括沉积循环，每个循环包括：
(i)以脉冲形式将前体馈送到所述反应空间以使所述前体吸附在所述衬底的表面上；
(ii)在步骤(i)之后，将RF功率施加于所述第二电极以在所述反应空间中产生等离子体，前体吸附的所述表面暴露于所述等离子体，由此在所述表面上形成子层；以及
(iii)在步骤(ii)中施加RF功率时将偏置电压施加于所述第二电极，参考所述第一电极的表面上的电位，所述偏置电压为负，
其中重复所述循环以沉积多个子层，直到由所述子层构成的膜具有所要厚度。
2.根据权利要求1所述的方法，其中所述偏置电压是DC电压。
3.根据权利要求1所述的方法，其中所述偏置电压是具有1MHz或更低频率的AC电压，其平均电压不为零。
4.根据权利要求1所述的方法，其中所述第一电极接地。
5.根据权利要求1所述的方法，其中步骤(ii)另外包括将RF功率施加于所述第一电极。
6.根据权利要求1所述的方法，其中在步骤(ii)中，所述等离子体是氢等离子体。
7.根据权利要求1所述的方法，其中所述偏置电压的平均值是10到1,000V。
8.根据权利要求1所述的方法，其中所述膜是氧化物膜、氮化物膜或碳膜。
9.根据权利要求1所述的方法，其中经历步骤(i)的所述衬底具有作为底层膜的聚合物膜或非晶硅膜，所述膜直接沉积于所述底层膜上。
10.根据权利要求1所述的方法，其中在步骤(iii)中，所述偏置电压在所述循环重复时逐渐减小。
11.根据权利要求9所述的方法，其中所述沉积循环是第一沉积循环，且所述PEALD另外包括第二沉积循环，每个第二沉积循环包括步骤(i)和(ii)，且在所述第一沉积循环之后不再实施步骤(iii)。
12.根据权利要求11所述的方法，其中所述PEALD另外包括中间沉积循环，所述中间沉积循环包括步骤(i)到(iii)，其中所述偏置电压在所述循环重复时逐渐减小，其中在所述第一沉积循环之后连续地实施所述中间沉积循环，且在所述中间沉积循环之后连续地实施所述第二沉积循环。
13.根据权利要求9所述的方法，其中所述第一沉积循环在所述膜的厚度达到10nm或更低时终止。
14.根据权利要求1所述的方法，其中反应气体和载运/稀释气体在整个步骤(i)到(iii)中连续馈送到所述反应空间。
15.根据权利要求1所述的方法，其中所述循环另外包括在每个步骤(i)和每个步骤(ii)之后的净化。
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