CN100537839C - 形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法 - Google Patents

形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法 Download PDF

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CN100537839C
CN100537839C CNB2004800194209A CN200480019420A CN100537839C CN 100537839 C CN100537839 C CN 100537839C CN B2004800194209 A CNB2004800194209 A CN B2004800194209A CN 200480019420 A CN200480019420 A CN 200480019420A CN 100537839 C CN100537839 C CN 100537839C
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B·A·瓦尔特斯卓
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Abstract

本发明包括形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法。在一个实施中，一种形成含掺杂磷的二氧化硅的层的方法包括：在沉积室中定位衬底。在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，在多个沉积循环中，将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上。第一和第二汽相反应物中的一个是PO(OR)3，其中R是烃基，并且第一和第二汽相反应物中的另一个是Si(OR)3OH，其中R是烃基。

Description

形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法
技术领域
本发明涉及形成含掺杂磷的二氧化硅的层的方法，并且涉及在制造集成电路中形成沟槽隔离的方法。
背景技术
在集成电路的制造中一种常用的材料是二氧化硅。可以将其以基本上100％纯的形式利用，或与包括性质调节掺杂剂的其它材料组合使用。因此，可以将二氧化硅在形成一层或多层中作为与其它材料的混合物利用，并且它可以占或者可以不占给定层的大多数。示例性材料是硼磷硅酸盐玻璃(BPSG)、磷硅酸盐玻璃(PSG)和硼硅酸盐玻璃(BSG)。典型地，这种材料的硼和/或磷原子各自的浓度为1原子％至4原子％的任何浓度，尽管也使用超过5％的原子％浓度。
由于半导体器件的几何尺寸持续缩小，这种趋势导致在横向尺寸上的收缩比纵向尺寸上的收缩更大。在某些情况下，纵向尺寸增大。无论如何，得到器件增加的纵横比(高度比宽度)，从而使得开发可以将介电和其它材料填充高纵横或逐渐增加纵横比的沟槽、通孔或其它台阶或结构的方法日益重要。一种典型的介电材料选择是含掺杂或未掺杂二氧化硅的材料，例如上面所述的那些材料。掺杂剂如硼和磷可以促进沉积层在更高温度下的回流，从而促进对在衬底上的开口更完全的填充。在形成二氧化硅层中可以利用各种反应物前体，例如，在美国专利6,300,219中公开的硅烷醇。
发明概述
本发明包括形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法。在一个实施中，一种形成含掺杂磷的二氧化硅的层的方法包括：在沉积室中定位衬底。在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，在多个沉积循环中，将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上。第一和第二汽相反应物中的一个是PO(OR)3，其中R是烃基，并且第一和第二汽相反应物中的另一个是Si(OR)3OH，其中R是烃基。
在一个实施中，一种形成含掺杂磷的二氧化硅的层的方法，该方法包括在沉积室中定位衬底。从包含其中R是烃基的PO(OR)3的第一汽相反应物中，将第一物种化学吸附至衬底的表面上，以在该室中向该表面上形成第一物种单层。使化学吸附的第一物种与包含其中R是烃基的Si(OR)3OH的第二汽相反应物接触，形成含Si和O的单层。在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，依次重复第一物种的化学吸附和化学吸附的第一物种与第二反应物的接触。
其它方面和实施是预期的。
附图简述
以下参考下面的附图描述本发明的优选实施方案。
图1是在根据本发明的一个方面的方法中半导体晶片片段的剖面示意图。
图2是图1的晶片片段在图1所示的方法之后的处理步骤下的视图。
图3是图2的晶片片段在图2所示的步骤之后的处理步骤下的视图。
图4是在根据本发明的一个方面的方法中半导体晶片片段的剖面示意图。
图5是图4的晶片片段在图4所示的方法之后的处理步骤下的视图。
图6是图5的晶片片段在图5所示的步骤之后的处理步骤下的视图。
图7是图6的晶片片段在图6所示的步骤之后的处理步骤下的视图。
优选实施方案详述
在一个实施中，一种形成含掺杂磷的二氧化硅的层的方法包括：在沉积室中定位其上将要被沉积的衬底。在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，在多个沉积循环中，将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上。第一和第二汽相反应物中的一个是PO(OR)3，其中R是烃基。第一和第二汽相反应物中的另一个是Si(OR)3OH，其中R是烃基。这可以通过原子层沉积(ALD)方法(例如，包括化学吸附和接触方法)，通过化学气相沉积(CVD)方法，和通过其它方法，以及通过这些方法与其它方法的组合来进行。此处使用CVD和ALD，参考于2002年4月25日提交的共同未决美国专利申请序列号10/133,947，标题为＂Atomic Layer Deposition Methods and Chemical Vapor DepositionMethods＂，并且将Brian A.Vaartstra列为发明人，该美国专利申请案目前对应于美国专利公开号2003-0200917。于2002年4月25日提交的所述美国专利公开号2003-0200917通过引用而全文结合在此，如同将其全部内容列出在此一样。在此提供的优选和理解具体采用的实例被理解为主要通过原子层沉积。
PO(OR)3的R烃基和Si(OR)3OH的R烃基可以相同或不同，并且无论如何在一个优选实施方案中，各自的R烃基仅含有1至5个碳原子。一个优选并且具体采用的PO(OR)3材料包括磷酸三乙酯。一种优选示例且具体采用的Si(OR)3OH材料包括三叔丁基硅烷醇。示例性的优选条件包括约50℃至约500℃的温度，并且更优选为约100℃至约300℃。示例性的压力条件是低于大气压的，优选为约10-7托至约10托，并且更优选为约10-4托至约1托。所述的条件可以包括第一和第二反应物中至少一个的等离子体产生，或者没有第一和第二反应物的等离子体产生。如果利用等离子体产生，这可以发生在沉积室的内部，和/或其外部。相信最优选的条件是没有第一和第二反应物的等离子体产生。
该条件可以对于形成具有非常低磷含量的含二氧化硅的层是有效的，所述的磷含量例如不超过0.5原子％，包括更低的量。备选地，该条件可以对形成具有至少1.0原子％磷，包括例如5.0或更大的原子％磷的含二氧化硅的层有效。
在所述含掺杂磷的二氧化硅的层的形成中，该方法可以除了第一和第二汽相反应物外，不向该室中引入任何汽相反应物。备选地，该方法可以包括：在第一和第二汽相反应物的至少某些所述分离脉冲的中间，引入不同于第一和第二汽相反应物的另一种汽相反应物。仅作为实例，示例性的另一种汽相反应物是含氧的，例如O2、O3和/或任何汽相含氧化合物。除了PO(OR)3流之外，已经确定臭氧脉冲，例如作为O2和O3的混合物，有利于更多的磷结合，例如，高于5原子％的磷结合，如果这是所期望的。
另一种示例性汽相反应物将是含硼的，于是含掺杂磷的二氧化硅的层也将包含硼，例如在制造BPSG或类BPSG材料中。示例性的含硼材料是B(OR)3。
所述交替和瞬时分离脉冲可以包括下列之一或组合：在分离脉冲中间，对室的抽气和/或用隋性气体(例如N2和/或任何稀有气体)对该室的吹扫，以除去未反应的前体/反应物。
一种用于形成含二氧化硅的层的现有技术描述于Hausmann等，RapidVapor Deposition of Highly Conformal Silica Nanolaminates，SCIENCEMAGAZINE，Vol.298，pp.402-406(2002)中。这种方法起初利用甲基铝(methyaluminum)反应物前体，例如三乙基铝或二甲基酰胺铝，其在衬底上形成初始的含铝层。然后，烷氧基硅烷醇，例如三(叔丁氧基)硅烷醇流向衬底。显然，铝的存在提供了自限制催化反应，由此含二氧化硅的层沉积至某个自限制厚度，该厚度为在100埃至700埃之间的任何厚度。换言之，持续地曝露于烷氧基硅烷醇没有导致含二氧化硅的层的持续生长。显然，与简单的类ALD方式相反，二氧化硅层的自限制生长是以某种催化方式发生，原因在于通过硅烷醇曝露/脉冲形成明显多于几层单层。无论如何，铝被结合到得到的层中，这可能不是所期望的。
虽然此处公开的本发明不排除它与类似Hausmann等人的方法一起使用，但是最优选的是，本发明的方法在所述含掺杂磷的二氧化硅的层的形成中，不向该室中引入任何汽相含铝反应物。此外，根据本发明优选的是，在所述含掺杂磷的二氧化硅的层的形成中，衬底没有铝。
在一个实施中，形成含掺杂磷的二氧化硅的层的方法至少包括某种ALD处理。仅仅作为实例，示例性的这种方法参考图1-3来描述。参考图1，将衬底10定位于任何适宜的沉积室(未显示)中。在一个示例性的实施方案中，衬底10是半导体衬底，例如包括某种材料12，所述的材料12优选包括至少某种半导体材料，并且当然可以包括多种材料和层。在本文件的上下文中，将术语“半导体衬底”或“半导体的衬底”定义为表示任何包括半导体材料的构造，包括但不限于大块半导体材料如半导体晶片(或者单独地，或者包括在其上的其它材料的组件)，以及半导体材料层(或者单独地，或者包括在其上的其它材料的组件)。术语“衬底”是指任何支撑结构体，包括但不限于上面所述的半导体衬底。衬底10具有表面14，如所示的，提供被羟基化的表面14(含有悬空的OH基)。同样预期其它的表面端接在此处所述的方法中是也有效的。如果羟基化，可以将这种表面在提供在沉积室中之前羟基化，或者在沉积室中羟基化。用于羟基化表面14的示例性的技术包括将该表面曝露于水蒸汽中。此外，该表面可以通过简单曝露于环境气氛中而自然羟基化。
参考图2，从例如如上所述的包含其中R是烃基的PO(OR)3的第一汽相反应物中，化学吸附第一物种，以在该室中向该羟基化表面上形成第一物种单层16。在图2中，这被描绘为包括变量“A”，作为构成层16的至少部分。优选的条件和其它属性如上对于首先描述的实施所述。
参考图3，化学吸附的第一物种已经与包含Si(OR)3OH的第二汽相反应物接触，其中R为烃基，以形成将包含Si和O的单层18。再次，优选条件如上对于第一实施所述。图3描绘的层18包括变量“B”，其中化学吸附的第一物种单层被描绘为A’，A’示例性地表示在用A化学吸附B中的A物种的某种变体，其中确切优选和典型的物种A和B未被确定。无论如何，第一物种的化学吸附和化学吸附的第一物种与第二反应物的接触是在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下依次重复的。典型并且优选的是，这样的化学吸附和接触是对衬底以交替和瞬时分离脉冲的方式进行的，例如如上在首先描述的实施中所述。
上面所述的实施是相对于PO(OR)3的表面化学吸附，接着包含Si(OR)3OH的第二汽相反应物暴露，并且由此，具体采用本发明的一个方面，尽管本发明的多个方面不必如此限制。
无论如何，本发明的方面可以优选用于在集成电路的制造中形成沟槽隔离的方法，例如如图4-7所示并且如参考图4-7所述。图4显示包含大块单晶硅的半导体衬底26或其它半导体材料衬底28。在半导体衬底28上形成掩模层30。这被描绘为包括衬垫氧化物层32和上覆的含氮化物层34，所述的氮化物如氮化硅。
参考图5，已经将隔离沟槽36和38通过掩模层30蚀刻至衬底28/26的半导体材料中。现在或其后，例如对于二氧化硅，可以通过将衬底26暴露于热氧化条件而提供热氧化物层或其它层，例如氮化硅(未显示)层。
参考图6，已经在半导体材料隔离沟槽36和38中形成了磷掺杂的含二氧化硅的层40。用于这样做的示例性技术包括：如上所述的在多个沉积循环中将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上，并且例如通过如上所述的化学吸附和接触方法。如所述，该沉积对于向掩模层30上沉积含磷掺杂的二氧化硅的层40是有效的，并且被描述为对于在隔离沟槽36和38中选择性沉积磷掺杂的二氧化硅的层40是无效的。在本文件的上下文中，“选择性/选择地沉积”是一种在衬底上沉积材料时，衬底的一个区域与另一个区域的沉积厚度比率至少为2:1的沉积。
例如如图6所示，该沉积对于完全地填充隔离沟槽36和38或不填充这样的隔离沟槽应该是有效的。例如如图7所示，可以连续进行沉积处理，例如如上任何一种所述，以完全填充这种沟槽。备选地，仅仅作为实例，可以将图6的构造在从掩模层30上除去所述材料之前或之后用另一种材料填充。
示例性的具体采用的实例利用磷酸三乙酯和三(叔丁氧基)硅烷醇作为第一和第二相应的汽相反应物。通过下面的方法在氮化硅衬里的沟槽之上沉积650埃的PSG保形层(8原子％磷)：使用每种反应物的各自两秒反应性脉冲，其中一秒氩吹扫，之后在反应物脉冲之间没有流动氩的情况下抽空三秒。在300℃进行600个完全的循环。没有使用臭氧。用于进料磷酸三乙酯和三(叔丁氧基)硅烷醇的相应鼓泡器/安瓿温度为50℃和40℃。
还用温度为60℃的磷酸三乙酯和温度为70℃的三(叔丁氧基)硅烷醇进行这种处理。在300个完全的循环后，这种磷酸三乙酯和三(叔丁氧基)硅烷醇的一(1)秒和0.5秒相应脉冲得到650埃的膜，从而提供的沉积速率为约2.2埃/循环。这稍高于首先具体采用的实例沉积，其沉积速率为1.1埃/循环。沉积的膜基本上没有碳，并且磷含量低于0.5原子％。在这种反应物温度下磷酸三乙酯暴露的时间越长，预期得到生长速度越高，并且提高在沉积膜中的磷含量。
在另一种具体采用的实例中，将来自60℃鼓泡器/安瓿的磷酸三乙酯进料至沉积室中的基材，时间1秒。其后是1秒钟的30sccm Ar流，接着在没有任何气体向其流动的情况下对该室进行3秒的抽空。然后，向该室中流入25sccm的O2/O3(5体积％至12体积％的O3)的混合流，时间2秒。其后是1秒钟的30sccmAr流，接着在没有气体进料至该室的同时，抽空3秒。然后，从60℃鼓泡器/安瓿向该室流入三(叔丁氧基)硅烷醇，时间2秒。其后是1秒钟的30sccm Ar流，再之后，在没有气体进料至该室的同时，抽空3秒。进行400个完全的循环，其中在所有处理的过程中的压力从0.24托改变至10-6托。这得到100埃厚的层，其具有结合其中的5.7原子％的磷。

Claims (61)

1.一种形成含掺杂磷的二氧化硅的层的方法，该方法包括：
在沉积室中提供衬底；并且
在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，在多个沉积循环中，将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上，第一和第二汽相反应物中的一个是PO(OR)3，其中R是烃基，并且第一和第二汽相反应物中的另一个是Si(OR)3OH，其中R是烃基。
2.权利要求1的方法，其中所述的条件包括原子层沉积。
3.权利要求1的方法，其中所述的条件对于形成具有不超过0.5原子％磷的含二氧化硅的层是有效的。
4.权利要求1的方法，其中所述的条件对于形成具有至少1.0原子％磷的含二氧化硅的层是有效的。
5.权利要求1的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，除了第一和第二汽相反应物外，不向该室中引入任何汽相反应物。
6.权利要求1的方法，该方法包括：在第一和第二汽相反应物的至少某些所述分离脉冲的中间，引入不同于第一和第二汽相反应物的另一种汽相反应物。
7.权利要求6的方法，其中所述的另一种汽相反应物是含氧的。
8.权利要求7的方法，其中所述的另一种汽相反应物包括O3。
9.权利要求6的方法，其中所述的另一种汽相反应物是含硼的，所述含掺杂磷的二氧化硅的层包含硼。
10.权利要求1的方法，其中PO(OR)3的R烃基仅含有1至5个碳原子。
11.权利要求1的方法，其中Si(OR)3OH的R烃基仅含有1至5个碳原子。
12.权利要求1的方法，其中PO(OR)3包括磷酸三乙酯。
13.权利要求1的方法，其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
14.权利要求1的方法，其中PO(OR)3包括磷酸三乙酯，并且其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
15.权利要求1的方法，其中所述的条件包括50℃至500℃的温度。
16.权利要求15的方法，其中所述的条件包括100℃至300℃的温度。
17.权利要求1的方法，其中所述的条件包括10-7托至10托的压力。
18.权利要求1的方法，其中所述的条件包括第一和第二反应物中的至少一个的等离子体产生。
19.权利要求1的方法，其中所述的条件没有第一和第二反应物的等离子体产生。
20.权利要求1的方法，该方法包括在分离脉冲的中间用惰性气体吹扫该室。
21.权利要求1的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，在衬底上没有铝。
22.权利要求1的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，不向该室中引入任何汽相含铝反应物。
23.权利要求1的方法，该方法包括形成具有均匀组成的所述含掺杂磷的二氧化硅的层。
24.一种形成含掺杂磷的二氧化硅的层的方法，该方法包括：
在沉积室中提供衬底；
从包含其中R是烃基的PO(OR)3的第一汽相反应物中，将第一物种化学吸附至衬底的表面上，以在该室中向该表面上形成第一物种单层；
使化学吸附的第一物种与包含其中R是烃基的Si(OR)3OH的第二汽相反应物接触，形成含Si和O的单层；并且
在对于在衬底上沉积含掺杂磷的二氧化硅的层有效的条件下，依次重复第一物种的化学吸附和化学吸附的第一物种与第二反应物的接触。
25.权利要求24的方法，其中提供的至少首先化学吸附第一物种的衬底表面为羟基化表面。
26.权利要求24的方法，其中所述的条件对于形成具有不超过0.5原子％磷的含二氧化硅的层是有效的。
27.权利要求24的方法，其中所述的条件对于形成具有至少1.0原子％磷的含二氧化硅的层是有效的。
28.权利要求25的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，至少在提供羟基化表面之后，除了所述的第一和第二汽相反应物外，不向该室中引入任何汽相反应物。
29.权利要求24的方法，该方法包括：在至少某些所述的重复化学吸附和接触的中间，引入不同于第一和第二汽相反应物的另一种汽相反应物。
30.权利要求29的方法，其中所述的另一种汽相反应物是含氧的。
31.权利要求30的方法，其中所述的另一种汽相反应物包括O3。
32.权利要求29的方法，其中所述的另一种汽相反应物是含硼的，所述含掺杂磷的二氧化硅的层包含硼。
33.权利要求24的方法，其中PO(OR)3的R烃基仅含有1至5个碳原子。
34.权利要求24的方法，其中Si(OR)3OH的R烃基仅含有1至5个碳原子。
35.权利要求24的方法，其中PO(OR)3包括磷酸三乙酯。
36.权利要求24的方法，其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
37.权利要求24的方法，其中PO(OR)3包括磷酸三乙酯，并且其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
38.权利要求24的方法，该方法包括在所述的重复化学吸附和接触的中间用惰性气体吹扫该室。
39.权利要求24的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，在衬底上没有铝。
40.权利要求24的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，不向该室中引入任何汽相含铝反应物。
41.权利要求24的方法，该方法包括在衬底中形成的半导体材料隔离沟槽中沉积含掺杂磷的二氧化硅的层。
42.权利要求24的方法，该方法包括形成具有均匀组成的所述含掺杂磷的二氧化硅的层。
43.一种在集成电路的制造中形成沟槽隔离的方法，该方法包括：
在半导体衬底之上形成掩模层；
通过掩模层蚀刻隔离沟槽至半导体衬底的半导体材料中；并且
在蚀刻隔离沟槽之后，在对于在隔离沟槽中沉积含掺杂磷的二氧化硅的层有效的多个沉积循环中，将第一和第二汽相反应物以交替和瞬时分离脉冲的方式引入至该室中的衬底上，第一和第二汽相反应物中的一个是PO(OR)3，其中R是烃基，并且第一和第二汽相反应物中的另一个是Si(OR)3OH，其中R是烃基。
44.权利要求43的方法，其中所述的沉积对于填充所述的隔离沟槽是有效的。
45.权利要求43的方法，其中所述的沉积不填充所述的隔离沟槽。
46.权利要求43的方法，其中所述的沉积循环对于在掩模层上沉积掺杂磷的含二氧化硅的层是有效的。
47.权利要求43的方法，其中所述的沉积循环对于在所述的隔离沟槽中选择性沉积含掺杂磷的二氧化硅的层是无效的。
48.权利要求43的方法，其中所述的沉积循环对于形成具有不超过0.5原子％磷的含二氧化硅的层是有效的。
49.权利要求43的方法，其中所述的沉积循环对于形成具有至少1.0原子％磷的含二氧化硅的层是有效的。
50.权利要求43的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，除了所述第一和第二汽相反应物外，不向该室中引入任何汽相反应物。
51.权利要求43的方法，该方法包括：在第一和第二汽相反应物的至少某些所述分离脉冲的中间，引入不同于第一和第二汽相反应物的另一种汽相反应物。
52.权利要求51的方法，其中所述的另一种汽相反应物是含氧的。
53.权利要求52的方法，其中所述的另一种汽相反应物包括O3。
54.权利要求51的方法，其中所述的另一种汽相反应物是含硼的，所述掺杂磷的含二氧化硅的层包含硼。
55.权利要求43的方法，其中PO(OR)3包括磷酸三乙酯。
56.权利要求43的方法，其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
57.权利要求43的方法，其中PO(OR)3包括磷酸三乙酯，并且其中Si(OR)3OH包括三(叔丁氧基)硅烷醇。
58.权利要求43的方法，该方法包括在分离脉冲的中间用惰性气体吹扫该室。
59.权利要求43的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，在衬底上没有铝。
60.权利要求43的方法，该方法在所述含掺杂磷的二氧化硅的层的形成中，不向该室中引入任何汽相含铝反应物。
61.权利要求43的方法，该方法包括形成具有均匀组成的所述含掺杂磷的二氧化硅的层。
CNB2004800194209A 2003-07-07 2004-06-30 形成含掺杂磷的二氧化硅的层的方法和在制造集成电路中形成沟槽隔离的方法 Expired - Fee Related CN100537839C (zh)

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US7790632B2 (en) 2010-09-07
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