CN1154422A - 形成铁电薄膜的方法及其设备 - Google Patents

形成铁电薄膜的方法及其设备 Download PDF

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CN1154422A
CN1154422A CN96121174A CN96121174A CN1154422A CN 1154422 A CN1154422 A CN 1154422A CN 96121174 A CN96121174 A CN 96121174A CN 96121174 A CN96121174 A CN 96121174A CN 1154422 A CN1154422 A CN 1154422A
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白镕求
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Abstract

一种在可涂敷性、结构精细度和组成的均匀性方面都是优越的铁电薄膜是通过由下列步骤组成的方法获得的:通过用RF能激发等离子体引发由多种元素组成的铁电反应物离解,使其能够参与沉积反应;建立最佳工艺条件,在该条件下,使通过激发等离子体由反应物的离解而得到的离子在高温低压下进行沉积作用;通过导管、集合管和喷头向反应器无损耗地供给反应物,集合管用于聚集反应物,喷头用于喷射混合的反应物;在反应器中沉积铁电薄膜,而从导管中清除残余气体。

Description

形成铁电薄膜的方法及其设备
本发明涉及形成半导体元件的方法,更具体的说,是涉及形成铁电体薄膜的方法以及用于形成它的设备。
在制造256M或1GDRAM或更大规模的高集成半导体元件时,一般用BST(barium strontium tetanode)、SAO(strontiumtetanode SrTIO3)、或BTO(barium tetanode SrTIO3)作为用于电容器薄层的铁电材料。此类铁电体薄膜的使用简化了生产过程,降低了生产成本,使得半导体元件可以大规模地集成。
一般为了制造高绝缘的BST、SAO或BTO薄膜,通常使用阴极真空喷镀法或溶胶--凝胶法,在这些方法中用粗反应物在有机溶剂中的溶液进行涂敷。
然而这些常规方法是不值得推荐的,因为通过这些方法得到的薄层用于高集成半导体元件时,在许多方面都存问题,包括在精细图案上的可涂敷性、结构的精细度和电可靠性。
对于BST薄层,近来已开发了化学蒸气沉积技术。然而它达不到适用于高集成半导体元件的铁电薄层所要求的目标。
因此,本发明的目的是克服上述现有技术的不足,提供一种形成具有优越的绝缘性的铁电薄膜的方法及其设备。
本发明的另一个目的是提供一种形成适用于制造高集成半导体元件的铁电薄膜的方法及其设备。
根据本发明的一个方面,形成铁电薄膜的方法包括下列步骤:通过用RF能激发等离子体引发由多种元素组成的铁电反应物离解,使其能够参与沉积反应;建立最佳工艺条件,在该条件下,使通过激发等离子体由反应物的离解而得到的离子在高温低压下进行沉积作用;通过导管、集合管和喷头向反应器无损耗地供给反应物,集合管用于聚集反应物,喷头用于喷射混合的反应物;在反应器中沉积铁电薄膜,而从导管中清除残余气体。
根据本发明的另一方面,形成铁电薄膜的方法包括下列步骤:通过用RF能激发等离子体引发由多种元素组成的铁电反应物离解,使其能够参与沉积反应;建立最佳工艺条件,在该条件下,使通过激发等离子体由反应物的离解而得到的离子在高温低压下进行沉积作用;使胺配位体与反应物化合,在高温低压下通过导管、集合管和喷头向反应器无损耗地供入化合的反应物,集合管用于聚集反应物,喷头用于喷射混合的反应物;控制导管、集合管和喷头的温度;在反应器中沉积铁电薄膜,而从导管中清除残余气体。
根据本发明的再一个方面,用于形成铁电薄膜的设备包括:确定沉积空间的腔体;腔体上面用于聚集反应物的集合管;用于将集合管中的反应物转化为气态并将其喷射到薄片上的喷头;围绕在喷头、薄片以及加热部件周围的阻挡导板,它用于阻止由喷头喷出的气体扩散得太宽以及阻止其过快地渗入真空部分;以及设置在薄膜上面作为RF电极的板(用于形成等离子体)。
参照附图通过下列实施方案的描述本发明的其它目的和方面将是显然的,其中:
图1是根据本发明第一实施方案用于形成BST铁电薄膜的的设备简图。
图2是根据本发明第二实施方案用于形成SAO或BST铁电薄膜的设备简图。
参照附图最好地理解本发优选实施方式的应用。
首先参照图1,图1示出了根据本发明第一实施方案沉积BST薄膜的设备。
如图1所示,根据本发明沉积BST薄膜的设备包括腔体10,腔体10里有薄片1,并且腔体10确定了在薄片1上沉积的内部空间。在腔体10的上面有集合管2,通过该管将反应物装入腔10的内部空间。与集合管2相连的气体喷头3安装在腔体10的内部,以便喷射气态反应物。其实,气体喷头3把从集合管2出来的用于薄膜的反应物转化为气体,并将其喷射到薄片1上。在腔体10里薄片1和喷头3的周围还有圆柱形阻挡板4。该阻挡导板作用是阻止由喷头3喷出的气体扩散得太宽或阻止其过快地渗入真空部分。薄片1上面有作为RF电极的板5,以便形成等离子体。
下面将描述用该设备沉积铁电BST薄膜的方法。
方便的是基本上分三个阶段来描述铁电BST薄膜的沉积方法:反应物以及它的供给;薄膜沉积作用;和再进行薄膜沉积作用。
首先描述反应物以及它的供给。
因为大部分Ba和Sr源本身在常温下保持固体状态,所以为了将其供给反应器,应该通过把它储存在等温室里将其加热到150--200℃。因此应想办法使源在热和化学方面稳定。为此将带有氨基的化学物质(BA,BC)例如NET3和NH3在某温度下加热。此时使该化学物质与Ba、Sr源接触,并且作为配位体通过用N2气(CA)鼓泡而与它们反应。这样带有氨基的Ba、Sr源升华并流入反应器。可以通过N2气(CA)、带有氨基的化学物质(BA,BC)和Ba、Sr源的加热温度控制Ba、Sr源的流速。
Ti本身可以用作Ti源,可以通过加热温度和N2气(CA)流速控制它流入反应器。
此外,向反应器供入选自N2O和O2气的氧化剂(CD)。
当升化的Ba、Sr、Ti源到达反应器时,为了使它们不再凝结,将它们在约200--250℃下加热。由各自的导管出来的Ba、Sr、Ti和N2O在集合管2混合在一起,然后被引入到喷头3。在喷头3里(通过它均匀地喷射升华的反应物),由于从加热器6传递过来的加热薄片1的热能可能发生气相反应,因此用冷却剂例如水、油、空气和N2气将喷头3的温度控制在200--250℃。
就薄膜的沉积过程来说而言,通过低压下等离子体激发作用将升华的多种反应物保持在高温,由此得到良好的铁电BST薄膜。
通过等离子激发技术可以降低反应物之间的反应活化能之差,在等离子激发技术中RF能被通到喷头3,并通过作为RF电极的板连杆传递给RF电极板5。因此在薄片1和RF电极之间产生等离子体,而与喷头3无关。
为了得到优质的BST薄膜,可以改变该方法的变量,包括例如喷头3和薄片1之间的距离,调节该距离使喷头3喷射出来的气体均匀地喷射到薄片1上。
此外,可以使RF电极板5离开薄片一定的距离,以便即使在较低的RF能下也很容易得到等离子体,而不考虑它与喷头3的距离。
当为了得到具有良好可涂敷性的沉积薄膜必须保持低压时,气体可能流动不均匀、产率将降低、等离子体扩散,为了防止这些现象,喷头3、加热器6周围的阻挡板4由电绝缘材料制成,例如陶瓷或石英。
因为大多数Ba、Sr、Ti源都含有大量的碳和水分,因此为了生产高质量的薄膜,必须将它们在约500℃或更高温度下从由N2O等离子体新生出来的高活性氧中除去。此时用直接与薄片1接触的加热块6在约500℃或更高温度下加热薄片1。
最后,将描述以薄膜到薄膜的方式再生产沉积的BST薄膜。
必须除去导管中的残余气体。为此,将抽吸的气体例如N2气或带有氨基的化学物质鼓入Ba、Sr、Ti源的管路,然后通过集合管2抽出来。此方法正好在BST薄膜沉积后进行,且抽吸的气体沿着下面的路线。
Sr管路的清除路线从N2气导管(CA)开始,其中带有氨基的化学物质(BA)被鼓入该管,通过Sr源的前体容器(BB)进入到集合管2,由集合管2通过清除线路7将气体抽出。
类似地,Ba管路的清除路线从另一个N2气导管(CA)开始,其中带有氨基的化学物质(BA)被鼓入该管。该清除气体流入Ba源的前体容器(BD),然后进入集合管2,最后通过清除线路7用泵抽出去。
对于Ti管路的清除路线来说,可以选用N2气导管(CA)、Ti源的前体容器(BE)、集合管2和清除线路7。
在所有的沉积过程中,可能在反应器的内表面上形成薄膜。为了使薄膜的沉积有更好的再生性,应根据,例如,就地等离子腐蚀原理除去不合要求的薄膜。
详细地说,把装在钢瓶(CB)中的CF4或C2F6或装在钢瓶(CE)中的O2充入反应器。把RF能施加到RF电极板上,以激发等离子体,然后用等离子体腐蚀可能沉积在加热器和RF电极板5上的薄膜。
此刻,使用胺配位体就地合成的作为反应物的Ba、Sr、Ti源前体与高温低压下的等离子体的激发作用一起大大地提高了铁电BST薄膜的质量。
与反应器无关,通过清除残余在气体路线里的反应物,可以提高再现性。
发现阻挡导板和RF电极板大大有助于增加沉积率。
参照图2,图2示出了根据本发明第一实施方案的沉积BST或SAO薄膜的设备。
如图2所示,根据本发明的沉积BST或SAO薄膜的设备包括:圆形或其它形状的腔体20。腔体20里有薄片1,并且腔体20确定了在薄片11上沉积的内部空间。在腔体20的上面有集合管12,通过该管将反应物装入腔体20的内部空间。与集合管12相连的气体喷头13安装在腔体20的内部,以便喷射气态反应物。其实气体喷头13把从集合管12出来的用于薄膜的反应物转化为气体并将其喷射到薄片11上。在腔体20里薄片11和喷头13的周围还有圆柱形阻挡导板14。该阻挡导板作用是阻止由喷头13喷出的气体扩散得太宽或阻止其过快地渗入真空部分。薄片11上面有作为RF电极的板15,以便形成等离子体。
在沉积薄膜的设备中,通过加热器16将薄片11加热到500--600℃,蒸发掉有机物和水分,得到稳定的SAO薄膜。
在约为1乇或更低的真空条件下,阻挡板导14显示了控制气体流动、增加参与沉积的气体部分和阻止等离子扩散得太宽的多种功能。
RF电极板15是网状的(其中直径1mm的丝以2--3mm的间隔排列),它的作用是激发等离子体,而与从喷头13喷射出的气态反应物的流动无关。通过使用板15,在0.5--1W/cm2下就可以引发多种反应物的离解。
喷头13与RF电极板15之间的间隔是提高沉积在薄片11上的薄膜的均匀性的重要因素。最好使该间隔保持在约10--15mm。RF电极板15与薄片11距离也确定在3--10mm。
用本发明第二实施方案的设备,可以沉积可靠的铁电SAO或TBO薄膜。方便的是基本上分三个阶段来描述该沉积方法:反应物以及它的供给;薄膜沉积作用;和薄膜沉积作用的再现性。
首行描述反应物以及它的供给。
通常用Sr(thd)2或Sr(i-o-pr)2作为Sr源,Ba(thd)3或Sr(i-o-pr)3作为Ba源。Ti(i-o-pr)4Ti源的代表。因为在常温下大部分Ba和Sr源本身保持固体状态,Ti源是液体状态,所以为了将其供给反应器,应该把前者变成流动状态。这可以通过在等温室里将其加热到150--200℃来实现。从而,使Sr源或Ba源升华。因此应想办法使这些源在热和化学方面稳定。为此将带有氨基的化学物质(BA,BC)例如NET3、NH3或NH2R(其中R是烷基)在某温度下例如50--100℃下加热。此时使该化学物质与Ba或Sr源接触,并且通过用N2气(CA)鼓泡作为配位体与其反应。这样升华的带有氨基的Ba或Sr源即使在高温、高压下在热和化学方面也是稳定的。
SAO或BTO薄膜的沉积率可以通过Ba或sr源的量、N2气(CA)的流速以及带有氨基的化学物质(BA,BC)和Ba或Sr源的加热温度来控制。
Ti(i-o-pr)4被用来提供Ti,并且可以通过加热温度和N2气(CA)流速控制它流入反应器。
此外,向反应器供入选自N2O和O2的氧化剂。
为了把升华的Ba或Sr源和升华的Ti源稳定地转移到反应器中,它们使用各自的气体导管,用于Ba或Sr源的导管在150--200℃下被加热,用于Ti源的导管在50--100℃下被加热。
当升化的Ba、Sr和Ti源到达反应器时,为了使它们不再凝结,将它们在约200--250℃下加热。由各自的导管出来的Ba、Sr、Ti和N2O(或O2)在集合管12混合在一起,然后被引入喷头13。在喷头13里(通过它均匀地喷射升华的反应物),由于从加热器6传递过来的加热薄片11的热能可能发生气相反应,因此,喷头13必须保持在约200--250℃。此刻,使冷却剂例如水、油、空气和N2气沿着板的最外路线(18-19-18)流动。
关于薄膜沉积过程而言,通过低压等离子体激发作用将升华的多种反应物保持在高温下,借此得到具有良好可涂敷性、精细结构和均匀组成的铁电BST薄膜。
当使用由C、H和O元素组成的有机物时,它们之间的沉积活化能存在很大差别。此外,如果用纯热能引发沉积反应的话,某些元素被少量沉积。
通过等离子激发技术可以降低反应物之间的这种差别,在等离子激发技术中RF能用于等离子激发作用。例如,如果将0.5--1W/cm2的低密度和频率为13.56MH的RF能作用在喷头13上的话,那么RF电极的板导杆(2--R)的电势与RF电极板15的电势相等,因为它们都是与喷头13连接在一起的。在这种情况下,接地的加热器16在RF电极板15(包括薄片)与加热器16之间形成等离子体,而与喷头13无关。
为了得到优质的BST薄膜,可以改变该方法的变量,包括例如喷头13和薄片11之间的距离。
此外,可以使RF电极板15离开薄片11一定的距离,以便即使在较低的RF能下也很容易地得到等离子体,而不考虑它与喷头3的距离。
为了得到良好涂敷性和无有机物和水的精细结构薄膜,必须在约1乇或更低的压力下。在此低压下,气体在喷头13和薄片11之间的流动可能不均匀、参与沉积的有效气体部分降低、等离子体扩散使SAO或BTO薄膜沉积到不合需要的位置。为了防止这些副作用,阻挡导板4由电绝缘材料制成的,例如陶瓷或石英,并且它离加热器为3--5mm。
因为大多数Ba、Sr、Ti源都含有大量的碳、氧、氢和水分,因此为了生产高质量的薄膜,必须将它们除去。这可以通过在约500℃或更高温度下加入氧化剂例如O2或N2O来简单地完成。此时用直接与薄片11接触的加热器6在约500℃或更高温度下加热薄片11。
最后,将描述以薄膜到薄膜或产品到产品的方式再生产SAO或BTO薄膜。
必须除去粘附在气体导管中的残余气体和沉积在RF电极板15上的SAO或BTO薄膜。首先,为了除去残余气体,把升华的带有氨基的化学物质鼓入Ba或Sr的管路,而Ti管路用N2气(CA)或N2载体气。清除气聚集在集合管2里,然后在预先确定的时间,例如,10秒或几分钟内通过清除线路17用泵将其抽出去,而不考虑反应器。清除气沿着下面的线路流动。
Ba或Sr管路的清除路线从N2气导管(CA)开始,其中带有氨基的化学物质(BA)被鼓入该管,通过Ba或Sr源的前体容器(BB)进入到集合管12,集合管12通过清除线路17将气体抽出。
类似地,Ti管路的清除路线从另一个N2气导管(CA)开始,其中带有氨基的化学物质(BA)被鼓入该管。该清除气流入到Ti源的前体容器(BC),然后进入到集合管12,最后通过清除线路7用泵抽出去。
在所有的沉积过程中,SAO或BTO薄膜可能在RF电极板15上形成。为了使薄膜的沉积有更好的再生性,在未装入薄膜的情况下可以通过,例如,在RF电极板15和加热器16之间吹入CF4或C2F6、NF3、SF4、CCl4和O2除去不合要求的薄膜,同时激发等离子。
通过上述方法,沉积过程中在薄片11上形成的等离子体的电势可以保持恒定,并且可以保证良好的再现性。
如上所述,该形成铁电体薄膜的方法及其设备的特征在于,使用带有胺配位体的就地合成的作为反应物的Ba、Sr、Ti源前体与高温低压下的等离子体的激发作用一起大大提高了铁电BST、SAO或BTO薄膜的质量,它们在结构精细度、可涂敷性、组成的均匀性和无杂质方面都是优越的。
根据本发明,不考虑反应器,通过清除残余在气路里的反应物,可以提高再现性。
本发明方法和设备的优点是,阻挡导板和RF电极板大大有助于增加沉积率。
此外,本发明的另一个优点是,可以防止由未完全反应而造成的副产品粘附在薄片上。
已经以举例的方式描述了本发明,应该理解所用的术语是为了说明本发明的实质而不是对它进行限制。
根据上述说明,本发明的许多改进和改变都是可能的。因此,应该理解,在所附权利要求书的范围内,本发明可以以除具体描述以外的其他方式实施。

Claims (19)

1、一种形成铁电薄膜的方法,该方法包括下列步骤:
通过用RF能激发等离子体引发由多种元素组成的铁电反应物离解,使其能够参与沉积反应;
建立最佳工艺条件,在该条件下,使通过激发等离子体由所说的反应物的离解而得到的离子在高温低压下进行沉积作用;
通过导管、集合管和喷头向反应器无损耗地供给所说的反应物,所说的集合管用于聚集所说的反应物,所说的喷头用于喷射混合的反应物;和
在所说的反应器中沉积铁电薄膜,而从导管中清除残余气体。
2、根据权利要求1的方法,其中所说的清除是通过用升华的带有氨基的化学物质或N2气进行的,所说的残余气用泵通过所说的集合管排出。
3、根据权利要求1的方法,其中将所说的导管在200--300℃下加热,以便防止离解的反应物和用于清除的气体的再凝结。
4、根据权利要求1的方法,其中将所说的喷头在200--250℃下加热,以便防止所说的反应物进行气相反应而形成微粒,并且所说的RF能为交变型。
5、根据权利要求1的方法,还包括下列步骤:用通过等离子体纯化的O2、CF4或C2F6、NF3和SF4腐蚀掉沉积在所说的反应器内不合要求的副产物。
6、根据权利要求1的方法,其中所说的反应物是其中的氨基作为配位体就地合成的物质。
7、根据权利要求6的方法,其中所说的氨基用NET3或NH2R作为载气就地合成的。
8、根据权利要求1的方法,其中所说的铁电薄膜是BST薄膜。
9、一种形成铁电薄膜的方法,该方法包括下列步骤:
通过用RF能激发等离子体引发由多种元素组成的铁电反应物离解,使其能够参与沉积反应;
建立最佳工艺条件,在该条件下,使通过激发等离子体由所说的反应物的离解而得到的离子在高温低压下进行沉积作用;
使胺配位体与所说的反应物化合,在高温低压下通过导管、集合管和喷头向反应器无损耗地供给化合的反应物,集合管用于聚集反应物,喷头用于喷射混合的反应物;
控制所说的导管、所说的集合管和所说的喷头的温度;和
在所说的反应器中沉积铁电薄膜,而从导管中清除残余气体。
10、根据权利要求9的方法,其中所说的铁电薄膜是SAO薄膜。
11、根据权利要求9的方法,其中所说的铁电薄膜是BTO薄膜。
12、根据权利要求9的方法,其中所说的清除是通过使用升华的带有氨基的化学物质或N2气进行的,所说的残余气用泵通过所说的集合管排除。
13、根据权利要求12的方法,其中将所说的导管在200--300℃下加热,以便防止离解的反应物和用于清除的气体的再凝结。
14、根据权利要求9的方法,其中将所说的喷头在200-250℃下加热,以便防止所说的反应物进行气相反应而形成微粒,并且所说的RF能为交变型。
15、根据权利要求9的方法,还包括下列步骤:用通过等离子体纯化的O2、CF4或C2F6、NF3和SF4腐蚀掉沉积在所说的反应器内不合要求的副产物。
16、一种用于形成铁电薄膜的设备,该设备包括:
确定沉积空间的腔体;
腔体上面用于聚集反应物的集合管;
用于将集合管中的反应物转化为气态并将其喷射到薄片上的喷头;
围绕在喷头、薄片以及加热部件周围的阻挡导板,它用于防止由喷头喷出的气体扩散得太宽以及防止其过快地渗入真空部分;和
薄片上面用于形成等离子体的RF电极板。
17、根据权利要求16的设备,还包括将集合管保持或控制在预先确定的高温下的装置,目的是使反应物不再凝结变成常温下在集合管中的其液相或固相。
18、根据权利要求16的设备,其中所述的RF电极板15是网状的,其中直径为0.5--1.5mm的丝以2--3mm的间隔排列。
19、根据权利要求16的设备,其中所说的阻挡导板由绝缘材料制成,并且它离放置所说的薄片的板为3--5mm。
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GB9620757D0 (en) 1996-11-20
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GB2305940A (en) 1997-04-23
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