CN101061255A - 低温SiN沉积方法 - Google Patents

低温SiN沉积方法 Download PDF

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CN101061255A
CN101061255A CNA2005800393940A CN200580039394A CN101061255A CN 101061255 A CN101061255 A CN 101061255A CN A2005800393940 A CNA2005800393940 A CN A2005800393940A CN 200580039394 A CN200580039394 A CN 200580039394A CN 101061255 A CN101061255 A CN 101061255A
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treatment zone
containing precursor
silicon
nitrogen
pressure
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阿吉特·P·帕仁吉佩
康展·张
布伦登·麦克杜格尔
韦恩·维雷布
米歇尔·巴顿
艾伦·戈德曼
萨默纳斯·内奇
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Applied Materials Inc
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Abstract

本发明公开了通过将含硅前驱物导入处理区中，排出处理区中包括含硅前驱物的气体，同时均匀逐渐降低处理区的压力，将含氮前驱物导入处理区中，并排出处理区中包括含氮前驱物的气体，同时均匀逐渐降低处理区的压力，在处理区内的衬底上沉积硅氮化物层。在排气步骤期间，压力降低相对于时间的斜率基本为常数。

Description

低温SiN沉积方法
技术领域
本发明的实施方式一般涉及衬底处理。更具体地，本发明涉及化学气相沉积工艺。
背景技术
化学气相沉积(CVD)薄膜用于在集成电路中形成材料的多层。CVD薄膜用作绝缘体、扩散源、扩散掩模和注入掩模、间隔物和最终钝化层。通常在设计具有特定的热量和质量传输特性的腔室中沉积所述薄膜以优化在衬底表面上物理性和化学性均匀的薄膜的沉积。腔室通常为较大集成设备的一部分以在衬底表面上制造多个元件。设计腔室以同时处理一个衬底或处理多个衬底。
由于器件几何尺寸减小以使集成电路能加快，预期降低沉积薄膜的热预算同时满足对高产率、新薄膜特性和低浓度的不相关物质的不断增长的需求。历来，在数个小时的时间周期内在低压条件下进行沉积的批式烘炉中以700℃或更高的温度执行CVD。可通过降低沉积温度达到低热预算。低温沉积需要采用低温前驱物或减少沉积时间。
已经使用硅卤化物做为低温硅源(参照Skordas，et al.，Proc.Mat.Res.Soc.Symp.(2000)606：109-114)。具体地，硅碘化物或四碘硅烷(SiI4)已与氨(NH3)一起使用以在低于500℃的温度下沉积硅氮化物。一旦超过阈值暴露，硅氮化物沉积速率基本独立于前驱物暴露。图1示出了与硅前驱物暴露时间成函数关系的归一化沉积速率如何渐近地到达最大值，并因此可估算前驱物暴露时间。所述温度为450℃。SiI4为具有0.5Torr的部分气压的含硅前驱物以及氨为含氮前驱物。
然而，SiI4为具有低挥发性的固体，其使低温硅氮化物沉积工艺困难。另外，与硅与氮含量化学计量比为约0.75的薄膜相比较，这些薄膜富含氮，具有硅与氮含量之比约0.66。这些薄膜还包含约16％到20％的氢。利用增强硼扩散通过正沟道金属氧化物半导体(PMOS)器件的栅极电介质以及利用偏离化学计量薄膜湿刻速率，这些材料中高氢含量可能对于器件性能是有害的。即，低温SiI4薄膜采用HF或热磷酸的湿刻速率比采用二氯硅烷和氨气在750℃沉积的硅氮化物薄膜的湿刻速率高3到5倍。另外，采用氨气作为含氮前驱物与硅卤化物一起用于硅氮化物薄膜的沉积产生诸如NH4Cl、NH4BR、NH4I和其他铵盐的形成。
另一种在低温下沉积硅氮化物薄膜的方法采用六氯乙硅烷(HCDS)(Si2Cl6)和氨气(参照Tanaka，et al.，J.Electrochem.Soc.147：2284-2289，美国专利申请公开号2002/0164890，和美国专利申请公开号2002/0024119)。图2示出了沉积速率在大暴露量下如何不渐近至恒定值，但单调增加而不达到饱和值，即使具有大暴露量。当它暴露于附加的气相HCDS中以在表面形成Si-Cl2并可能形成SiCl4时，表面化学吸收的HCDS逐渐分解。发现引入SiCl4和HCDS可略微降低腔室中HCDS的分解。用于该实验的含氮前驱物为氨。
当HCDS分解时，在衬底上可能不会出现沉积薄膜厚度的不均匀。还可能出现晶圆到晶圆薄膜厚度的变化。薄膜化学计量退化。所述薄膜富含硅并包含大量氯。这些偏差可导致最终产品中的漏电。为了防止HCDS分解，已试验了限定HCDS的部分压力和暴露时间。美国专利申请20020164890描述了控制腔室压力至2Torr并采用大流速的载气以降低HCDS部分气压。然而，为了在超过每周期2的沉积速率下得到表面的饱和，需要诸如30秒的长暴露时间。如果降低该暴露时间，则沉积速率可降低至每周期1.5以下。
通过在晶圆上维持对流气流以均匀分布反应物还可改善具有HCDS的衬底表面饱和。在美国专利5,551,985和6,352,593中对此进行了描述。
低压硅氮化物沉积的另一问题为前驱物的凝聚以及腔室表面上的反应副产物。由于这些沉积物从腔室表面分离并变得易碎，它们可能污染衬底。由于盐的蒸发和升华温度，铵盐形成物更有可能在低温硅氮化物沉积时形成。例如，NH4Cl在150℃蒸发。
因此，极需阻碍铵盐形成并采用有效的前驱物和高效的工艺条件用于低温硅氮化物沉积。
发明内容
本发明主要提供一种用于在处理区内的衬底上沉积包含硅和氮的层的方法。根据本发明的实施方式，该方法包括步骤：将含硅前驱物导入至处理区中，在包括含硅前驱物的处理区中排出气体同时均匀地逐渐降低处理区的压力，将含氮前驱物导入处理区中，以及在包括含氮前驱物的处理区中排出气体同时均匀地逐渐降低处理区的压力。根据本发明的一方案，在排气步骤期间压力降低相对时间的斜率基本为常数。
附图说明
因此以上方式所述本发明的特征可以更详细的理解，将参照实施方式对以上的简单概述进行对本发明更具体的描述，其中在附图中示出了部分实施方式。然而，应当注意附图仅示出了本发明的典型实施方式，并因此不能认为是本发明范围的限定，本发明可允许其他等同的有效实施方式。
图1为归一化沉积速率与硅源暴露时间的函数关系图(现有技术)；
图2为对于两种温度的沉积速率与压力的函数关系图(现有技术)；
图3为压力与时间函数关系图；
图4为用于沉积硅氮化物薄膜的元件的流程图；
图5为沉积速率和晶圆内部(WiW)不均匀度与温度的函数关系图；
图6为晶圆不均匀度与压力的函数关系图。
具体实施方式
本发明提供用于包括硅氮化物薄膜低温沉积的衬底处理的方法和设备。将具体描述含硅前驱物、含氮前驱物和其他工艺气体。接着，将描述工艺条件。最后，将描述实验结果和优点。本发明可在从位于加利福尼亚的Santa Clara的应用材料公司购买得到的FlexStar(tm)腔室、CA或在此处具体说明的条件下配置用于衬底处理的任意其他腔室中进行。在美国专利第6,352,593号、美国专利第6,352,594号、美国专利申请第10/216,079号和美国专利申请第10/342,151号中描述了详细的设备信息，在此引入其全部内容作为参考。用于导入前驱物的载气包括氩气和氮气。在工艺中用于清洗步骤的清洗气体包括氩气和氮气。
含硅前驱物
用于低温硅氮化物沉积的含硅前驱物为六氯乙硅烷和二氯硅烷。可选择含硅前驱物，原因在于它在室温下为液态或固态，其在预热温度下容易蒸发或升华。其他含硅前驱物包括硅卤化物，诸如SiI4、SiBr4、SiH2I2、SiH2Br2、SiCl4、Si2H2Cl2、SiHCl3、Si2Cl6和更一般地SiXnY4-n或Si2XnY6-n，其中X为氢或有机配位体以及Y为卤素诸如Cl、Br、F或I。也可选择较高阶硅烷盐，但一般前驱物的挥发性和热稳定性随着分子中硅原子数增加而降低。由于尺寸、热稳定性或其他特点，可选择有机成分，并且该有机成分包括任意直链或支链烷基组，诸如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、替代的烷基组，及其异构体诸如异丙基、异丁基、仲丁基、叔丁基、异戊烷、异己烷等。还可选择芳基组，其包括苯基和奈基。可选择烯丙基组和替代的烯丙基组。适合用于低温沉积应用的含硅前驱物包括乙硅烷、硅烷、三氯硅烷、四氯硅烷和双(叔丁胺)硅烷。SiH2I2还可适合用作前驱物，原因在于与其他前驱物相比，它与含氮前驱物发生强烈的放能和放热反应。
含氮前驱物
氨为用于低温硅氮化物沉积最常用的氮源。可选择烷基胺。替代物包括二烯丙基胺和三烷基胺。具体的前驱物包括三甲胺、叔丁胺、二烯丙基胺、甲胺、乙胺、丙胺、丁胺、烯丙胺、环丙胺和类似烷基胺。也可选择联氨、基于联氨衍生物和叠氮化物诸如烷基叠氮化物、叠氮化铵及其他。替代地，可采用原子氮。原子氮可由等离子体中的二原子氮气形成。该等离子体可在独立于沉积反应器的反应器中形成并经由电场或磁场传输至沉积反应器中。
基于沿着处理区的表面形成的不期望沉积的类型，还可选择含硅或含氮前驱物。具有低熔点的副产物残留比具有高熔点的副产物残留更容易挥发并从腔室排出。
沉积的工艺条件
图3和图4一起示出了如何操作腔室压力同时将前驱物、载气和清洗气体从腔室导入和排出的示意图。在清洗步骤401的时间t0时，腔室压力为沉积期间腔室最低压力P0。在含硅前驱物步骤402的时间t1时，含硅前驱物和可选载气导入腔室，该腔室压力快速上升至P1。在腔室压力P1下含硅前驱物的可选载气持续供应至时间t2。在从t2到t3进行的清洗步骤403期间，通过控制导入至腔室中的前驱气体和可选载气的减少并控制导入至腔室的清洗气体，以及控制排气阀的开口，得到腔室压力逐渐降低至P0。在含氮前驱物步骤404的时间t3时，含氮前驱物和可选载气导入腔室，腔室压力快速上升至P1。在腔室压力P1下，含氮前驱物和可选载气持续供应至t4。在从t4到t5进行的清洗步骤405期间，通过控制导入至腔室的前驱气体和可选载气的减少并控制导入至腔室的清洗气体，以及控制排气阀的开口，得到腔室压力逐渐降低至P0。在清洗步骤403和405期间，压力降低相对于时间的斜率基本为常数。步骤403和405的斜率可相似或不同，取决于前驱物的选择、衬底支架的温度、或其他设计条件。
导入处理区的初始高密度的前驱物使包括位于衬底表面上的开口的衬底表面快速饱和。如果高密度的前驱物留在腔室中的时间过长，则具有前驱物成分的不止一层将粘附在衬底表面。例如，在从系统清洗前驱物之后，如果过多的含硅前驱物残留在衬底表面，则生成的薄膜将具有不期望的高硅密度。处理区受控的逐渐降低的压力有助于维持沿着衬底表面的化学物的均匀分布，同时促使无关前驱物和载体从区域排出，同时利用附加的清洗气体诸如氮气或氩气清洗系统。处理区受控的压力的逐渐降低还防止在压力快速降低下常见的温度下降。
前驱物步骤402和404包括将前驱物导入腔室中。该前驱物步骤还包括导入诸如氮或氩的载气。另外，固定容积的前驱物可在预热区中加热，并导入处理区中以沿着衬底表面提供前驱气体均匀分布的饱和层。
可基于多种因素选择用于导入前驱气体和用于清洗所述气体的时间。可加热衬底支架至需要调整前驱物暴露时间以避免沿着腔室表面化学沉积的温度。在气体导入和清洗结束时的处理区压力可能影响时间选择。前驱物需要不同的时间量以沿着衬底表面完全化学吸收，而不是由可能改变生成薄膜的化学成分的过量化学物完全覆盖。前驱物的化学特性，诸如它们的化学质量、生成热或其他特性可能影响需要移动化学物通过系统的时间或沿着衬底表面的化学反应需要的长度。沿着腔室表面的沉积物的化学特性可能需要额外的时间清洗系统。在示例性实施方式中，用于导入前驱物和可选载气的时间周期从1秒变化到5秒，以及用于清洗步骤的时间周期从2秒到变化到10秒。
HCDS或DCS为优选的含硅前驱物。部分压力HCDS由生成的副产物和前驱物的成本限定。前驱物导入的优选摩尔分数为0.05到0.3。氨为优选的含氮前驱物，其也具有优选的进气摩尔分数0.05到0.3。
在软件控制下，通过操作诸如进气阀和出气阀的工艺硬件可控制处理区的压力。如图3所示，该工艺的系统的压力可从0.1Torr变化到30Torr。在沉积工艺中，腔室的处理区内的清洗压力的最低值为约0.2到2Torr，而在约2到10Torr下前驱物和载气可导入至腔室中。可调节衬底支架的温度至约400℃到650℃。
尤其是当选择室温下不可能是气体的的前驱物时，气体导入腔室可包括预热前驱物和/或载气。该气体可预热至约100到250℃以获得用于输送至处理区的充足蒸气压力和蒸发速率。可能需要加热SiI4高于约180℃。预热前驱物输送系统有助于在输送管道、处理区和腔室的排气装置中避免前驱物的凝结。
用于减少铵盐形成的工艺
可采用五种方法以减少铵盐形成和处理区的污染。一般地，通过从处理区去除氢卤化合物或通过利用使盐与气态烯烃或炔物质接触形成后去除盐，该机构使铵盐的形成最小。
首先，可利用诸如乙炔或乙烯的HY受主作为添加剂。在沉积前驱物混合物中包括HY受主允许盐有效地从反应器去除并可有助于除去从含硅或含氮前驱物离解的卤素原子。其他HY受主添加剂包括可为卤代或非卤代的烯烃、诸如降冰片烯(norborene)和亚甲基环戊烯的应变环系统，以及诸如SiH4的甲硅烷基氢化物。采用有机添加剂还可有益于沉积工艺原因在于可选择添加剂以调整加入薄膜的碳。碳加入薄膜的控制为期望的原因在于调整的碳含量降低湿刻速率，改善SiO2的干刻选择性，降低介电常数和折射系数，提供改善的绝缘性质，并且还可减少漏电。利用调整的碳添加，还可获得高的拐角刻蚀选择性。
第二，诸如硅烷的甲硅烷基氢化物添加剂可用作HI受主。包括HI受主通过限制NH4I形成降低处理区中铵盐的副作用。
第三，作为含硅前驱物和HI受主的化合物可用于将硅提供给工艺中并有效地从腔室去除盐。适合的含硅前驱物包括具有SiXnY4-n或Si2XnY6-n化学式的物质。
第四，可采用除氨外的氮源作为含氮前驱物，从而免除了用于形成铵盐的原材料。例如，与采用氨时相比，当烷基胺用作氮源时，将产生较少的HY。当用作含氮前驱物时，三烷基胺在热力学上更期望并且不产生任何HY。
最后，HY接收的诸如环丙基组或烯丙基组的一部分可结合诸如胺的氮源以得到最终的诸如环丙胺或丙烯胺的双功能化合物。该方法减少了将第三成分添加至前驱气体入口的必要。它还增加了HI受主结合HY受主的可能性。在温度低于500℃，该方法还是尤其期望的。
所述五种方法可以任何方式独立地采用或结合使用以有助于降低铵盐形成。
实验结果
在前驱物没有部分分解的情况下，如图3和图4所述，改进传统的清洗系统以使处理区压力逐渐并均匀降低导致较高级别的前驱物表面饱和。图5示出了晶圆到晶圆的不均匀度(百分比)和沉积速率(/周期)与从450℃到550℃采用HCDS和氨作为前驱物的沉积温度如何相关。图6示出了在导入前驱物气体期间从0.2Torr到7Torr的压力如何影响晶圆到晶圆的不均匀度。利用HCDS和氨在550℃沉积薄膜。傅立叶变换红外光谱分析表明所述薄膜为Si3N4。薄膜的覆盖率超过95％。该工艺还产生不超过1％的氯含量。沉积速率在590℃时增加至2/周期并在470℃降低至0.8/周期。在较低温度下硼扩散通过生成的薄膜也降低。下表1概述了在550℃时附加的实验结果。
  参数   值  注释
  沉积速率   1.5-1.6/周期  低于饱和值
  晶圆内部不均匀度(WiWNU)   ＜±1.5％  R/2M
  反射系数   1.99  ＞300薄膜
  化学计量   Si：N～0.74  化学计量比
  杂质  H～8％ Cl～0.9％   原子％
  表面粗糙度  Ra～3.7   ～417薄膜
  湿刻速率  31.5/分钟   100∶1 HF，2分钟
 222/分钟   热H3PO4，0.5分钟
  收缩  ～4.3％   850℃，60分钟N2退火
  应力  450MPa拉力   退火后1620MPa
  覆盖率  ～100％   40∶1AR深沟槽
  微负载  0-5％   由SEM分辨率限定
  金属污染  全反射X射线荧光分析(TXRF)分辨极限   包括Ti
  薄膜中微粒  ＜50(0.2μm)   100薄膜，SP-1
表1.在550℃沉积的硅氮化物薄膜的测试结果。
导入诸如氢气或乙硅烷的载气或添加剂也改变生成薄膜的性质。表2示出了观察到的沉积速率、反射系数、硅与氮之比，以及在利用不同的分裂方法形成的薄膜中观察到的氢百分比。通过利用不包含氮的载气或包括添加剂的载气，可提高薄膜的氢含量和硅与氮之比。
  分裂  速率/分钟   (反射系数)R.I.   Si∶N   [H]At.％
  基线(w/N2)  14.5   1.800   0.65   20.2
  基线(w/Ar)  13.5   1.799   0.72   20.5
  低压(0.5Torr)  6.76   1.811   0.65   19.1
  NH3∶Si源～20∶1  17.9   1.807   0.65   19.7
  NH3∶Si源～4∶1  12.0   1.795   0.72   20.1
  氢添加剂  14.3   1.084   0.65   19.4
  乙硅烷添加剂  20.6   2.386   1.0   11.3
表2.在基线条件下和采用添加剂沉积的薄膜的性质。
有多种方法控制碳添加。在表3中，A为硅前驱物(HCDS)，B为氮前驱物(氨)，以及C为添加剂(叔丁胺)。
  方法  速率/周期   反射系数 WER/分钟
  A→B  1.9   1.95 13
  A→C  1.0   1.93 1
  A→B→C  1.65   1.93 3
  A→C→B  1.85   1.94 4
  A→B→A→C  1.70   1.92 4
  A→33％B+67％C  1.80   1.93 4
  A→67％B+33％C  2.0   1.94 9
  A→50％+50％C2H4  1.9   2.0 7
表3.用于不同沉积工艺的沉积速率、反射系数和湿刻速率。
用A→C→A→C顺序沉积的薄膜包含高达20％的碳，而A→B→A→B顺序薄膜不包含任何碳。其他方法在薄膜中得到中间值的碳。如果在顺序A→50％B+50％C中用叔丁胺代替C2H4，则薄膜的湿刻速率将适当降低同时沉积速率和反射系数基本不受影响。另外，碳含量为探测极限(小于1原子百分比)。
以控制量导入碳以100∶1 HF提高湿刻速率为1.5到10的倍数。利用具有碳加入的干刻速率降低为1.25到1.5倍。通过利用乙烯、叔丁胺和二烯丙基胺作为HY受主结合Si2Cl6和氨观察到这种提高的湿刻速率。
发现导入SiCl4和HCDS以降低HCDS分解形成SiCl2的可能性。
在此描述的前驱物还可应用在硅氧化物的低温沉积中。该工艺可采用具有远程等离子体的O2、O3、H2O、H2O2、N2O或Ar和O2作为氧化剂。前驱物还可应用于氮氧化物的低温沉积中，其中N2O2用作氮和氧源。
虽然上述针对本发明的实施方式，但在不偏离本发明的基本范围内，可设计本发明的其他及进一步的实施方式，并且本发明的范围由以下的权利要求书所限定。

Claims (20)

1.一种用于在处理区内的衬底上沉积包含硅和氮的层的方法，包括：
将含硅前驱物导入到所述处理区中；
排出所述处理区中包括所述含硅前驱物的气体，同时均匀地逐渐降低所述处理区的压力；
将含氮前驱物导入到所述处理区中；以及
排出所述处理区中包括所述含氮前驱物的气体，同时均匀逐渐降低所述处理区的压力。
2.根据权利要求1所述的方法，其特征在于，进一步包括维持衬底支架在400℃到650℃的温度。
3.根据权利要求1所述的方法，其特征在于，所述处理区的所述压力为0.2到10Torr。
4.根据权利要求1所述的方法，其特征在于，在每个排气步骤期间压力降低相对于时间的斜率基本为常数。
5.根据权利要求4所述的方法，其特征在于，在所述排气步骤期间所述压力降低相对于时间的所述斜率基本相同。
6.根据权利要求4所述的方法，其特征在于，用于导入所述含硅前驱物的时间周期和用于导入所述含氮前驱物的时间周期为1到5秒。
7.根据权利要求4所述的方法，其特征在于，用于排出所述处理区中包括所述含硅前驱物和所述含氮前驱物的气体的时间周期为2到20秒。
8.根据权利要求1所述的方法，其特征在于，在导入所述含硅前驱物时所述处理区中的压力为0.2到10Torr，以及在导入所述含氮前驱物时所述处理区中的压力为0.2到10Torr。
9.根据权利要求1所述的方法，其特征在于，在导入所述含硅前驱物之前所述处理区中的压力为0.2Torr，以及在导入所述含氮前驱物之前所述处理区中的压力为0.2Torr。
10.根据权利要求1所述的方法，其特征在于，所述含氮前驱物选自包含氨、三甲胺、叔丁胺、二烯丙基胺、甲胺、乙胺、丙胺、丁胺、丙烯胺和环丙胺的组。
11.根据权利要求1所述的方法，其特征在于，含硅前驱物选自包括乙硅烷、硅烷、三氯硅烷、四氯硅烷和双(叔丁胺)硅烷的组。
12.一种用于在处理区内的衬底上沉积包括硅和氮的层的方法，其特征在于，包括：
预热含硅前驱物和含氮前驱物；
将含硅前驱物导入至所述处理区中；
排出在所述处理区中包括所述含硅前驱物的气体，同时均匀逐渐降低所述处理区的压力；
导入含氮前驱物至所述处理区内；以及
排出在所述处理区中包括所述含氮前驱物的气体同时均匀逐渐降低所述处理区的压力。
13.根据权利要求12的方法，其特征在于，将所述含硅前驱物和所述含氮前驱物预热至100到250℃。
14.根据权利要求12所述的方法，其特征在于，在所述排气步骤期间通过控制导入至所述处理区的清洗气体量以及通过控制连接所述处理区的排气阀降低所述处理区的压力。
15.根据权利要求12所述的方法，其特征在于，所述含氮前驱物选自包括氨、三甲胺、叔丁胺、二烯丙基胺、甲胺、乙胺、丙胺、丁胺、丙烯胺和环丙胺的组以及所述含硅前驱物选自包括乙硅烷、硅烷、三氯硅烷、四氯硅烷和双(叔丁胺)硅烷的组。
16.根据权利要求12所述的方法，其特征在于，所述处理区中的所述衬底支架维持在400到650℃的温度。
17.根据权利要求12所述的方法，其特征在于，所述处理区的压力为0.2到10Torr。
18.一种用于在处理区中在衬底上沉积包括硅和氮的层的方法，其特征在于，包括：
将含硅前驱物导入至所述处理区中；
排出所述处理区中包括所述含硅前驱物的气体，同时降低所述处理区的压力从而压力降低相对于时间的斜率基本为常数；
将含氮前驱物导入至所述处理区中；以及
排出在所述处理区中包括所述含氮前驱物的气体，同时降低所述处理区的压力从而压力降低相对于时间的斜率基本为常数。
19.根据权利要求18所述的方法，其特征在于，用于导入所述含硅和含氮前驱物的时间周期为1-5秒，以及用于排出包括所述含氮和含硅前驱物的时间周期为2-20秒。
20.根据权利要求18所述的方法，其特征在于，所述处理区的压力为0.2到10Torr。
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