CN1389910A - 利用原子层淀积形成薄膜的方法 - Google Patents

利用原子层淀积形成薄膜的方法 Download PDF

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CN1389910A
CN1389910A CN02107879A CN02107879A CN1389910A CN 1389910 A CN1389910 A CN 1389910A CN 02107879 A CN02107879 A CN 02107879A CN 02107879 A CN02107879 A CN 02107879A CN 1389910 A CN1389910 A CN 1389910A
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CN1312757C (zh
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金营宽
朴泳旭
李承换
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Samsung Electronics Co Ltd
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Abstract

本发明提供一种利用原子层淀积(ALd)形成薄膜的方法。提供一种具有单反应空间的ALD反应器。可以在所述ALD反应器的单反应空间中同时装载一批衬底。然后,在单反应空间中引入含反应剂的气体,在单反应空间内,反应剂的一部分化学吸附到该批衬底的上表面上。然后,从单反应空间中排除未被化学吸附的反应剂。根据本发明的一个实施例,引入含反应剂气体后,在单反应空间内稀释未被化学吸附的反应剂,以便于排除未被化学吸附的反应剂。

Description

利用原子层淀积形成薄膜的方法
本发明涉及半导体器件领域，具体涉及一种利用原子层淀积(ALd)形成半导体器件薄膜的方法。
形成现有高集成半导体器件薄膜要求许多严格的制造条件，例如低热预算，优异的台阶覆盖，膜厚的精确控制，简单工艺偏差及低颗粒污染。
例如低压化学汽相淀积(LPCVd)、等离子增强化学汽相淀积(PECVD)等常规CVD类方法，不再适于形成现有技术器件的薄膜，无法满足制造要求。例如，按典型CVD方法，薄膜是在较高温度淀积的。由于可能会对器件产生不良热影响，所以不希望这样。另外，CVD薄膜常常有例如厚度不均匀，即器件表面上厚度偏差或颗粒污染等缺点。
至于LPCVD，LPCVD薄膜中氢的含量一般较高，其台阶覆盖经常无法接受。
现已提出了原子层淀积(ALD)工艺代替这种常规薄膜形成技术。这种ALD工艺能在比常规CVD类方法低的温度下实施，而且还表现出优异的台阶覆盖。
美国专利6,124,158中公开了一种这样的ALD方法。这里，引入第一反应剂，与被处理表面反应，形成反应物质的键合单层。引入第二反应剂，与表面反应，形成希望的薄膜。在工艺周期的每一步骤后，都用惰性气体净化反应室，防止除表面外的反应。一般说，由于例如维护制造设备的缘故，反应剂的供应和净化在同样的压力下进行。
然而，这种常规ALD技术也存在几个缺点，例如，由于如原子层的较低生长速率引起的问题等造成的低产量。另外，例如行波型反应器等常规ALD反应器的反应空间设计得非常小，减小了净化副产物等的净化量。常规ALD反应器每次操作仅处理一、两片晶片，一般说，单个反应器一次操作仅处理一个衬底。这些缺点导致这些常规ALD技术难以付诸实际应用，经济上无法接受，即无法批量生产。
近来，为提高ALD工艺的产量，人们又做了几种尝试。美国专利6,042,652公开了一种。这里，ALD反应器包括多个组件和多个反应空间(工作台)，即用多个组装件隔离的空间。例如，下组件设置在上组件之下，由此在两者间形成一个反应空间(一工作台)，仅仅能容纳一个半导体衬底。
然而，由于每个反应空间(工作台)小且是间隔开的，即彼此隔离，每个衬底只能一个一个插入反应空间(工作台)。所以，很难利用自动晶片传送机构装/卸多个晶片。因此，要花相当长的时间装/卸晶片。另外，可以装载和处理的晶片数仍不够多。
因此，显然需要一种新颖具有高产量的ALD方法，能够克服上述问题，同时能提供高质量的薄膜。
本发明提供一种利用原子层淀积(ALD)形成薄膜的方法。提供一种具有单反应空间的反应器。一批衬底可以同时装载到该反应器的单反应空间中。
然后，将含反应剂气体引入到单反应空间内，在该单反应空间中，部分反应剂被化学吸附到该批衬底或晶片的上表面上。然后，从该单反应空间中排除未被化学吸附的的反应剂。
根据本发明的一个实施例，引入含反应剂气体后，在该单反应空间中稀释未被化学吸附的的反应剂，以便于未被化学吸附的反应剂的排除。
另外，根据本发明的另一实施例，公开了一种形成薄膜的方法，其中提供一种具有单反应空间的反应器。向反应空间中引入都具有处理表面的多个晶片。多个晶片的处理表面面向基本相同的方向。将第一反应剂引入到反应空间内，使部分第一反应剂化学吸附到多个晶片的处理表面上以备进行ALD。然后，从反应空间中排除第一反应剂的未被化学吸附的部分。然后，向反应空间中引入第二反应剂。另外，一部分第二反应剂化学吸附到多个晶片中的每一个的处理表面上。然后，从反应空间中排除第二反应剂的未被化学吸附的部分。
从以下结合附图对本发明优选实施例的详细介绍中，更容易理解本发明的上述和其它目的、特点和优点。
图1是根据本发明一个实施例的ALD反应器的示意剖视图。
图2是展示根据本发明一个实施例的ALD各步骤的ALD反应器压力的曲线图。
图3A-3D展示了根据本发明一个实施例形成ALD薄膜的各工艺步骤。
图4是展示根据本发明一个实施例的工艺条件的曲线图。
图5是展示根据本发明一个实施例进行的ALD工艺的结果的曲线图。
图6是展示根据本发明一个实施例进行的ALD工艺的结果的曲线图。
本发明一般期待一种利用ALD技术来制造薄膜的方法，通过该方法，与常规ALD技术相比，产量明显提高。
在以下说明中，记载了数字化的具体细节，以便于彻底理解本发明。然而，所属领域的普通技术人员应认识到，可以不用这些具体细节实施本发明。某些情况下，未具体展示已知工艺步骤和技术，以避免混淆本发明。
下面将介绍根据本发明一个实施例利用ALD技术形成薄膜的方法。
参见图1，该图示出了具有单反应空间12的ALD反应器10，反应空间12在处理管11内。为简便起见，省略了反应器10的其它部件，例如加热器等。ALD反应器10优选为立式炉反应器(垂直取向)，与常规LPCVD炉类似，如美国专利5,217,340和5,112,641所示。然而，任何其它类型的反应器，例如水平取向的反应器，只要适于实施本发明，都可作替代品，而不会脱离本发明的精神和范围。
根据本发明，反应空间12可以是放置衬底15(或晶片)，进行ALD的各工艺步骤的空间。另外，本发明中，单反应空间12不是隔开或隔离的。这不同于美国专利6,042,522和6,015,590中所示的在ALD反应器中有多个(隔开的)反应空间常规反应器的反应空间。在这些常规ALD反应器中，具体说在美国6,015,590中所述的反应器中，由于多个(隔开的)反应空间中的每个都有非常窄的载面，减小了反应空间容各积，降低了净化效率，可以装在每个反应器中的衬底数非常小，例如每个反应空间中一、两个衬底。另外，由于上述结构上的局限，常规ALD反应器的这一点限制了可以装在反应器中的衬底总数。例如，美国专利6,042,652所示形成每个反应空间的组件本自会在反应器内占用大量空间或容积。这些也严重降低了ALD工艺的产量。
然而，本发明中，由于炉式ALD反应器10具有未隔开的大容积单反应空间12，所以ALD反应器10中可以容纳衬底1百(100)片以上，如图1所示。所以，一次ALD操作要处理的衬底数可以明显增加(产量显著提高)。
为处理衬底15，在其上形成ALD薄膜，一批14衬底15基本上同时装入ALD反应器10的单反应空间12，如图1所示。本发明中，一批14是指装入反应器10以进行ALD操作从而在衬底15上形成薄膜的衬底总数。根据本发明的一个实施例，一批14优选地包括约125-135片衬底。每片衬底15的上表面优选地都具有处理表面17。
按本发明的ALD工艺，装/卸衬底15期间，优选利用图1所示的自动(即，非人工式)晶片传送机构18向ALD反应器10中装载一批14衬底15。这种自动晶片传送机构18可以是美国专利5,217,340和5,112,641中公开的那种。然而，可以采用任何适于实施本发明的自动晶片传送机构，仍在本发明的精神和范围内。
换言之，本发明中，由于一次ALD操作的所有产品衬底15都可以放在单反应空间12中，而不分布在反应器的几个反应空间中，所以利用晶片传送机构18可以自动地很快地装/卸一批14衬底15。具体说，一批14衬底按预定方式排列，插在舟19中。舟19一般由石英或其它常规材料制成，其内表面上有多个凹槽，用于容纳各衬底15。将装有一批14衬底的舟19装入ALD反应器10，于是便按图1所示的方式，将一批14衬底15同时装入ALD反应器10的单反应空间12中。这里，基本上所有衬底15的上表面17(处理面)都面向自动晶片传送机的同一方向。
于是，与例如美国专利6,015,590中公开的ALD技术等常规ALD技术相比，在产量方面具有明显的优势，在上述美国专利中，晶片的上表面面相相反的方向，所以自动晶片传送器将十分不方便或不可能。所以，按常规的ALD技术，仅仅可以在每个反应空间中一次一次地装少量衬底，多数为一片。其原因是衬底需要分布于反应器的数个空间内，这种分布几乎是不可能或很难一次全部完成。美国专利6,042,652中公开的常规ALD技术也一样，如背景部分所介绍的，多个圆形半导体衬底只能一个一个地传送到反应空间(工作台)中。整个装载过程要花很长时间，极大地降低了产量，所以限制了ALD工艺的商业应用。
如图3A所示，按常规ALD技术的方式，将第一反应剂40或含第一反应剂气体通过例如ALD反应器40的供气管线(未示出)等图1所示入口16引入单反应空间12。在单反应空间12内，第一反应剂40的一部分化学吸附到一批14半导体衬底15的处理表面17上。如图2所示，较好在约0.1乇和约0.5乇间的第一预定压力P1下进行配给步骤31。
另一方面，本发明中，为了进一步提高ALD的产量，需要减少ALD的净化时间。原因是净化时间一般与反应器的容积有关。由于本发明采用具有大容积的炉式反应器，净化量实质大于例如美国专利6,042,552或6,015,590中所示的行波型设备等其它常规ALD技术。
为克服这方面的问题，根据本发明的一个实施例，引入第一反应剂40后，为有效地减少净化时间，在从ALD反应器10中排除第一反应剂40中的未被化学吸附的部分之前，在单反应空间12中，稀释第一反应剂40的未被化学吸附的部分，这里，第一反应剂40的未被化学吸附的部分包括物理吸附的反应剂，即第一反应剂40物理地附着于其上，并松散地固定于ALD反应器10内第一反应剂40的化学吸附部分上或任何残留的反应材料上。
关于图2所示的稀释步骤33，如图1所示，ALD反应器10包括与排气管25相连的压力控制阀21或用于从ALD反应器10中排除第一反应剂40的稀释的未被化学吸附的部分的粗管。排气管25与用于将从第一反应剂40的未被化学吸附的部分排出到外边的泵23相连。稀释步骤33期间，控制阀21基本上关闭，惰性气体通过入口16供应到反应器10中，第一反应剂40到ALD反应器10的引入基本停止。即，降低ALD反应10的排气管线25的传导性。
或者，稀释步骤33期间，将其量明显大于第一反应剂40的量的惰性气体引入ALD反应器10，同时停止向反应器10引入第一反应剂40。
较好是，如图2所示，在第一反应剂40的未被化学吸附的部分的稀释期间，反应器压力从第一预定压力P1提高到第二预定压力P2，第二预定压力P2大于第一预定压力P1。第二预定压力P2较好是第一预定压力P1的约1.5倍。
这些步骤允许在非常短的时间内，例如几秒内，稀释反应器10中的第一反应剂40的未被化学吸附的部分，所以与常规ALD技术相比，净化步骤32期间，显著减少总净化时间，提高净化效率。该稀释过程明显降低了ALD反应器10中第一反应剂40的未被化学吸附的部分的分压。所以，在反应剂40已被稀释，第一反应剂40的未被化学吸附的部分被排除后，仅有很少量第一反应剂40的未被化学吸附的部分留在反应器10内，所以提高了净化效率。另外，由于稀释了第一反应剂40，所以可有效地防止第一反应剂40间的混杂。
然后，如图3B所示，在引入第二反应剂(配给步骤35)，利用化学交换形成图3D所示希望的ALD薄膜44之前，从单反应空间12中排除(抽空)被稀释的第一反应剂40的未被化学吸附的部分。第一反应剂40的未被化学吸附的部分的排除较好是利用泵23抽吸反应器10进行，从而将反应器10内的压力降低到第三预定压力P3(见图2)。第三预定压力P3低于配给步骤31的第一预定压力。第三预定压力P3较好是第一预定压力P1约0.5倍。
该步骤期间，到第三预定压力P3的压力下降，通过停止或减少惰性气体的引入，并打开控制阀21实现。即，提高排气管线的传导性。
现参见图3C，向反应空间12引入第二反应剂42，第二反应剂42中的一部分化学吸附到一批14衬底15的处理表面17上，发生化学交换。自然，稀释步骤37较好在第二反应剂42的配给步骤35之后进行。
现参见图3D，在排除步骤34期间，利用上述与应用于第一反应剂40相同的方法，从反应空间12排除第二反应剂42的未被化学吸附的部分。
可以重复上述引入第一和第二反应剂40、42和从反应空间排除反应剂41、42的未被化学吸附的部分的步骤，实现希望的膜厚。
应注意，本发明建议的净化方法与反应剂的类型无关，因而可应用于形成各种ALD薄膜。所述ALD薄膜例如可以是Al2O3、TiO2、ZrO2、HfO2、Ta2O5、Nb2O5、CeO2、Y2O3、SiO2、In2O3、RuO2或IrO2构成的氧化层。其它例子如下：SrTiO3，PbTiO3，SrRuO3，CaRuO3，(Ba，Sr)TiO3，Pb(Zr，Ti)O3，(Pb，La)(Zr，Ti)O3，(Sr，Ca)RuO3，(Ba，Sr)RuO3，掺Sn的In2O3(ITO)，掺Fe的In2O3，或掺Zr的In2O3构成的复合氧化物；SiN，NbN，ZrN，TiN，TaN，Y3N5，AlN，GaN，WN或BN构成的氮化物层；WBN，WSiN，TISiN，TaSiN或AlTiN构成的复合氮化物层；Si，Al，Cu，Ti，Ta，Mo，Pt，Ru，Rh，Ir，W或Ag构成的金属层；Al，W，Ti或Co的硅化物层；及金属硅酸盐材料(M1-xSixO2)。这里，金属“M”可以是铪(Hf)，锆(Zr)，钽(Ta)，钛(Ti)，铯(Cs)，或铝(Al)。所属领域的技术人员应理解，所列例子是不详尽的或不排它的，不想以任何方式限制所要求的本发明的范围。例1
利用本发明的ALD工艺淀积SiN膜。所用反应剂是由间接等离子体(remote plasma)(400W)激活的DCS(SiCl2H2)和NH3气体。淀积温度是375℃，反应剂流量是：DCS为500sccm，NH3为2000sccm。关于排除未被化学吸附的反应剂之前的稀释，向反应器中引入5000sccm的N2气体。DCS供应、DCS净化、NH3供应和NH3净化中每步的时间和压力示于表1，并另外示于图4中。另外，图5示出了上述ALD工艺的结果。
                                        表1
  项        DCS配给           DCS净化         NH3配给            NH3净化
  稀释   排除   稀释   排除
压力(乇)   ＜0.1→2.0   2.0   2.0→＞10  ＞10→＜0.1  ＜0.1→0.25     0.25    0.25→＞10  ＞10→＜1.0
时间(秒)     7.5   10     4     6     1.5     10     4     6
根据上述ALD工艺的生长速率是1埃/周期，可以实现良好的ALD处理特性。
另外，已观察到，不用本发明的净化方法，会发生以下问题。第一，如果在与反应剂的配给步骤期间的压力相同的压力下，用例如Ar或N2等惰性气体进行净化步骤，则大量惰性气体会留在反应器内。这样便会降低反应剂的分压。因此，用于下一配给步骤的反应剂配给时间会加长。此外，净化时间也会增加。第二，如果在像本发明的实施例那样的抽吸前不稀释，便通过抽吸进行净化步骤，则净化会花相当长的时间。例2
在室温下将HCD(Si2Cl6)存放在起泡器中，并用500sccm的N2气作载气引入反应器。然后，用5000sccm的N2气稀释未被化学吸附的反应剂，然后从反应器中抽掉(排除)未被化学吸附的反应剂，进行净化。然后，供应2000sccm的间接等离子体(400W)NH3，并通过用5000sccm的N2气稀释未被化学吸附的反应剂，然后，从反应器中抽掉未被化学吸附的反应剂，进行净化。
此时，向反应器供应HCD  20秒。反应器压力从0.1乇变到2乇，然后保持在2乇。净化期间的压力在稀释步骤(4秒)从2乇变到10乇，然后，在抽吸期间(6秒)降低到0.1乇。NH3的供应(30秒)和净化(4+6秒)按与上述相同的方式实施。图6示出了上述ALD工艺的结果。
生长速率为2.3埃/周期，可以实现良好的ALD处理特性。
上述本发明的一些特征如下所述：
1、配给步骤期间和净化步骤期间反应器的压力可以不同。
2、不同反应剂的每个配给步骤的反应器压力可以基本相同或不同。
3、净化步骤可以包括稀释步骤和排除或抽空步骤，稀释步骤期间，反应器压力从反应剂配给步骤期间的压力上升，排除或抽空步骤期间，其压力下降到低于反应剂配给期间的压力。
利用这些特征，可以实现以下效果。
1、每种反应剂的配给步骤与分压和时间相关(如Langmuirer所示的反应剂暴露依赖关系)。因此，通过增大反应剂配给期间所供应反应剂的分压，处理时间可以缩短。
2、不同于保持恒定压力的常规ALD工艺，通过抽吸进行了净化后，完成每种反应剂的配给步骤。因此，希望的压力可以由低压得到。
3、在大容积反应器中实施净化时，首先供应惰性气体，以稀释反应剂。然后，进行抽吸，以便在短时间内达到希望的净化效果。
总之，本发明具有优于常规ALD技术的许多优点，克服了常规ALD技术的许多缺点。例如，本发明显著提高了ALD工艺的产量。具体说，根据本发明的优选实施例，由于本发明的炉式ALD反应器具有未隔开的大容积单反应空间，所以一次可以容纳和处理衬底100片以上，明显多于任何其它常规ALD技术。另外，由于所有用于ALD工艺的产品晶片都可以放在单反应空间中，而不是分布在数个反应空间内，所以成批衬底的装/卸可利用自动晶片传送机械自动快速完成。另外，在从反应空间中排除未被化学吸附的反应剂之前，在单反应空间中稀释未被化学吸附的反应剂，所以可以显著缩短净化时间，提高净化效率。
除这些优点外，本发明的ALD反应器比常规ALD反应器成本低，容易维护。所以，本发明的ALD工艺将产量和可制造性提高到了可以利用ALD进行批量生产的程度。
上面已利用优选实施例介绍和展示了本发明的原理。但应理解，在不背离这些原理的的情况下，可以对本发明的设置和细节进行改进。我们要求落在以下权利要求书精神和范围内的所有改进和变化的权利。

Claims (41)

1.一种利用原子层淀积形成薄膜的方法：
提供具有单反应空间的反应器；
将一批衬底同时装载在反应器的单反应空间内；
向单反应空间中引入含反应剂的气体，在单反应空间，将反应剂的一部分化学吸附到衬底的上表面上；及
从单反应空间中排除未被化学吸附的反应剂。
2.根据权利要求1的方法，还包括，引入含反应剂的气体后，稀释在单反应空间内的未被化学吸附的反应剂。
3.根据权利要求2的方法，其中在第一预定压力下进行所述引入含反应剂的气体的步骤，在第二预定压力下进行所述稀释步骤，其中第二预定压力大于第一预定压力。
4.根据权利要求3的方法，其中第一预定压力介于约0.1乇到约0.5乇之间。
5.根据权利要求3的方法，其中所述第二预定压力是第一预定压力的约1.5倍。
6.根据权利要求2的方法，其中在第一预定压力下进行所述引入含反应剂的气体的步骤，
其中所述去除步骤包括抽吸反应器，从而将反应器压力降低到第三预定压力，及
其中第三预定压力低于第一预定压力。
7.根据权利要求6的方法，其中第三预定压力是第一预定压力的约0.5倍。
8.根据权利要求1的方法，其中所述装载步骤包括利用自动晶片传送机械传送所述一批衬底。
9.一种利用原子层淀积形成薄膜的方法：
在反应器内提供半导体衬底；
以第一预定压力向反应器中引入含反应剂的气体，将反应剂的一部分化学吸附到衬底表面上；
稀释在反应器内的未被化学吸附的反应剂，使反应器的压力升高到第二预定压力；及
从反应器中排除稀释的未被化学吸附的反应剂。
10.根据权利要求9的方法，其中第一预定压力介于约0.1乇到约0.5乇之间。
11.根据权利要求9的方法，其中所述第二预定压力大于第一预定压力的约1.5倍。
12.根据权利要求9的方法，其中通过抽吸反应器进行所述排除步骤，从而将反应器压力降低到第三预定压力，
其中第三预定压力低于第一预定压力。
13.根据权利要求12的方法，其中第三预定压力低于第一预定压力的约0.5倍。
14.根据权利要求9的方法，其中反应器包括与排除稀释的未被化学吸附的反应剂的排气管线相连的压力控制阀，其中所述稀释步骤包括，在基本上停止向反应器引入含反应剂的气体的同时，基本上关闭控制阀，并向反应器供应惰性气体。
15.根据权利要求9的方法，其中反应器包括与排气管线相连的压力控制阀，其中所述稀释步骤包括，在停止向反应器引入气体反应剂的同时，以实际高于气体反应剂的量向反应器供应惰性气体。
16.一种利用原子层淀积形成薄膜的方法：
在单反应器内设置多个晶片；
以第一预定压力向单反应器中引入气体反应剂，将反应剂的一部分化学吸附到多个衬底的上表面上；
将在单反应器内的未被化学吸附的反应剂稀释到第二预定压力；及
从单反应器中排除稀释的未被化学吸附的反应剂，
其中所述第二预定压力高于第一预定压力。
17.根据权利要求16的方法，其中反应器包括与排气管线相连的压力控制阀，其中所述稀释步骤包括，在停止向反应器引入气体反应剂的同时，基本上关闭控制阀，并向反应器供应惰性气体。
18.根据权利要求16的方法，其中反应器包括与排气管线相连的压力控制阀，其中所述稀释步骤包括，在停止向反应器引入气体反应剂的同时，以实际高于气体反应剂的量向反应器供应惰性气体。
19.根据权利要求16的方法，其中第一预定压力介于约0.1乇到约0.5乇之间。
20.根据权利要求16的方法，其中所述第二预定压力大于第一预定压力的约1.5倍。
21.根据权利要求16的方法，其中通过抽吸所述处理室进行所述排除步骤，从而将反应器压力降低到第三预定压力，
其中第三预定压力低于第一预定压力。
22.根据权利要求21的方法，其中所述第三预定压力低于第一预定压力的约0.5倍。
23.根据权利要求16的方法，其中通过抽吸所述处理室进行所述排除步骤，从而将反应器压力降低到第三预定压力，
其中第三预定压力低于第一预定压力。
24.根据权利要求16的方法，其中反应器是炉式反应器，其中基本上所有衬底的上表面都面对自动晶片传送器的相同方向。
25.根据权利要求16的方法，其中多个衬底的数量大于一百。
26.根据权利要求16的方法，其中反应器有一个用于原子层淀积单反应空间，使所有衬底都装在该单反应空间内。
27.一种形成薄膜层的原子层淀积方法，包括：
a)在处理室内插入一个或更多个半导体衬底；
b)以第一预定压力向反应器中引入第一气体反应剂，反应剂的一部分化学吸附到一个以上衬底的表面上；
c)通过向处理室内注入惰性气体，将反应室内的压力增大为高于第一预定压力；
d)从所述处理室中排除未被化学吸附的的第一反应剂；
e)以第二预定压力向反应器中引入第二气体反应剂，从而利用化学交换形成单原子金属层；
f)稀释反应器中的未被化学吸附的反应剂，使反应器压力升高；及
g)从所述处理室中排除未被化学吸附的反应剂。
28.根据权利要求27的方法，其中第一预定压力基本与第二预定压力相同。
29.根据权利要求27的方法，其中第一预定压力不同于第二预定压力。
30.根据权利要求27的方法，其中所述第一和第二稀释步骤期间，反应器压力分别升高到不小于第一和第二预定压力的约1.5倍。
31.根据权利要求27的方法，其中通过将所述处理室抽吸到实际低于第一或第二预定压力的第三预定压力，实施所述排除步骤。
32.根据权利要求27的方法，其中所述单原子层是由Al2O3、TiO2、ZrO2、HfO2、Ta2O5、Nb2O5、CeO2、Y2O3、SiO2、In2O3、RuO2或IrO2构成的氧化层。
33.根据权利要求27的方法，其中单原子层是由SrTiO3，PbTiO3，SrRuO3，CaRuO3，(Ba，Sr)TiO3，Pb(Zr，Ti)O3，(Pb，La)(Zr，Ti)O3，(Sr，Ca)RuO3，(Ba，Sr)RuO3，掺Sn的In2O3(ITO)，掺Fe的In2O3，或掺Zr的In2O3构成的复合氧化物。
34.根据权利要求27的方法，其中单原子层是由SiN，NbN，ZrN，TiN，TaN，Y3N5，AlN，GaN，WN或BN构成的氮化物层。
35.根据权利要求27的方法，其中单原子层是由WBN，WSiN，TiSiN，TaSiN或AlTiN构成的复合氮化物层。
36.根据权利要求27的方法，其中单原子层是由Si，Al，Cu，Ti，Ta，Mo，Pt，Ru，Rh，Ir，W或Ag构成的金属层。
37.根据权利要求27的方法，其中单原子层是Al，W，Ti或Co的硅化物层。
38.根据权利要求27的方法，其中单原子层是金属硅酸盐材料(M1-xSixO2)。这里，金属“M”可以是铪(Hf)，锆(Zr)，钽(Ta)，钛(Ti)，铯(Cs)，或铝(Al)。
39.根据权利要求27的方法，还包括重复步骤(b)-(g)中的至少一步的步骤。
40.一种形成薄膜的方法，包括：
a)提供具有单反应空间的反应器；
b)在所述反应空间中装入多个具有处理表面的晶片，其中所述晶片的处理表面面向基本相同的方向；
c)在所述反应空间中引入第一反应剂，其中第一反应剂的一部分化学吸附到多个晶片的每一个的处理表面上；
d)从所述反应空间中排除第一反应剂的未被化学吸附的部分；
e)在所述反应空间中引入第二反应剂，其中第二反应剂的一部分化学吸附到多个晶片的每一个的处理表面上；
f)从所述反应空间中排除第二反应剂的未被化学吸附的部分。
41.根据权利要求40的方法，还包括重复步骤(c)-(f)中至少一步的步骤。
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