CN101609858A - 薄膜沉积方法 - Google Patents
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Abstract
本发明公开了一种薄膜沉积方法，包括：在反应室中平行放置作为阳极的第一电极板和作为阴极的第二电极板，所述第二电极板面向所述第一电极板的表面具有牺牲层；在所述第一电极板面向所述牺牲层的表面放置基板；通入刻蚀气体；将所述第一电极板接地，向第二电极板施加直流负电压，将所述刻蚀气体电离为等离子体刻蚀所述牺牲层，在所述基板表面沉积薄膜。本发明的薄膜的沉积方法能够改善薄膜的性能特别是稳定性以及大面积沉积薄膜的均匀性。
Description
技术领域
本发明涉及光伏太阳能电池技术领域，特别涉及一种沉积薄膜的方法。
背景技术
近年来，由于能源的日益短缺，可再生绿色能源的开发利用越来越受到人们的关注。这其中尤以太阳能的利用特别受到世人的普遍青睐。作为太阳能转换媒介的光伏(photovoltaic)太阳能电池和大面积光伏模块的开发引起了广泛关注。在众多太阳能电池产品中，氢化非晶硅和纳米晶硅薄膜太阳能电池以其低成本、低能耗、可大面积沉积在玻璃或轻薄易于铺设安装的柔性衬底上等优势，代表着光伏技术的发展趋势，随着光伏器件在商业和住宅设施中的广泛应用，显示出巨大的潜力。
氢化非晶硅或纳米晶硅薄膜太阳能电池具有多膜层的结构，一个典型的薄膜硅太阳能电池包括玻璃基板、前后两个电极以及其间的p-i-n型光电转换单元。p-i-n型光电转换单元包括p型掺杂的p层、本征非掺杂型的i层和n型掺杂的n层。光电转换的过程发生在由基于本征氢化硅的半导体材料构成的i层之中，p层和n层的作用是在i层中建立内置电场，以便收集i层中产生的光致载流子。根据已知的使用氢化非晶硅和纳米晶硅及其合金的太阳能电池的结构，p型、本征i型和n型膜层的材料是基于非晶硅和/或纳米晶硅的材料。p-i-n型光电转换单元的光电转换效率在很大程度上取决于非掺杂的硅基薄膜i层的稳定性。
传统的形成氢化非晶硅薄膜i层的方法是采用等离子体增强化学气相沉积法(PECVD)工艺，图1为说明等离子体增强化学气相沉积工艺沉积薄膜方式的示意图，如图1所示，真空室10中置有两个极性相反的平行板状电极，分别为激励电极(阴极)11和接地电极(阳极)12，它们之间的区域17是等离子体的激励形成区域。激励电极11置于盒罩16中，盒罩16中用来限制等离子体反应区域和反应气体(原气体混合物)的流向。在盒罩16上开有进气口19，用来提供含有需沉积物质的反应气体。真空室10具有出气口18，用于将反应后的气体从真空室10中排出。激励电极11具有适当密度的通孔，其背后放置一个与盒罩16相连的喷淋板13，可使反应气体被均匀地输送进整个等离子体区域17，因此激励电极11表面不能放置基板，基板15通常被放置在接地电极12表面。为了使沉积的膜层具有良好的均匀性，载有基板15的接地电极12背面置有一个加热器14，使基板15达到并维持在设定的温度范围内。采用射频(RF)功率源为激励电极11提供能量，向反应室中通入含有薄膜沉积物质的反应气体，利用辉光放电将反应气体电离为等离子体，等离子体反应生成的薄膜前期物质沉积在基板15表面形成膜层。
PECVD工艺虽然具有工艺简单、沉积效率高的特点，但是在大面积(例如面积大于0.7m2)高速率沉积氢化硅薄膜时，均匀性会显著地下降。而且，等离子体沉积薄膜中的电子缺陷密度和均匀性难以得到较好的控制，例如在低温下(小于230℃)利用硅烷和氢气的源气体混合物沉积的非晶硅和纳米晶硅的薄膜，该硅基薄膜的结构中会含有大量的多氢硅键，影响基于氢化非晶硅的薄膜在光照下的稳定性，极大地限制了基于非晶硅太阳能电池的终极转换效率。
发明内容
本发明的目的在于提供一种薄膜沉积方法，能够改善薄膜的性能特别是稳定性以及大面积沉积薄膜的均匀性。
为达到上述目的，本发明提供的一种薄膜沉积方法，包括：
在反应室中平行放置作为阳极的第一电极板和作为阴极的第二电极板，在所述第二电极板面向所述第一电极板的表面具有牺牲层；
在所述第一电极板面向所述牺牲层的表面放置基板；
通入刻蚀气体；
将所述第一电极板接地，向第二电极板施加直流电压，将所述刻蚀气体电离为等离子体对所述牺牲层进行刻蚀，在所述基板表面沉积薄膜。
优选的，所述直流电压值为-150伏～-1000伏。
可选的，在所述第一电极板和第二电极板之间还放置网状第三电极板，在施加直流电场的同时，所述第一电极板和/或第二电极板和/或第三电极板上施加一个或多个交变电场。
所述交变电场由包括低频、射频(RF)、极高频(VHF)的电源提供。
所述刻蚀气体包括氢气H2。
所述刻蚀气体中含有与牺牲层物质成分相同的元素，且当牺牲层厚度为零时，所述基板表面不发生薄膜沉积。
所述刻蚀气体中氢气的浓度大于50％，其余气体中至少有一种气体含有卤族元素，包括氟气F2，SiF4、SiH2Cl2、HF、HCl、Cl2、BF3、NF3、SF6中的一种或多种，以及惰性气体中的一种或多种。
可选的，所述第一电极板和所述第二电极板之间的距离为1厘米～10厘米。
所述反应室内部的气体压力为1mbar～10mbar，基板的温度维持在100℃～260℃。
所述牺牲层的材料为硅、氢化硅、锗、氢化锗、氢化硅锗合金或其他半导体材料，包括上述材料的卤化物合金。
与现有技术相比，本发明具有以下优点：
本发明的薄膜沉积方法在反应室内平行相对放置阴极和阳极，在阴极表面具有牺牲层，该牺牲层作为沉积薄膜的原材料层，阳极面向牺牲层的表面放置基板，在阴极和阳极之间施加直流电场，将刻蚀气体电离激发为等离子体，等离子体对牺牲层进行刻蚀，被刻蚀而剥离的牺牲层物质向阳极方向扩散移动，沉积在基板表面形成薄膜。这种由刻蚀导致沉积的方法不依赖外界提供的原气体来沉积薄膜，薄膜沉积的前期物质的产生与沉积本身都在同一个局部的(local)等离子体区域发生，与基板或反应室的大小无关，从根本上解决了大面积薄膜沉积的均匀性问题。由于采用直流电场进行等离子体激发，远比通常使用的射频(RF)或极高频(Very High Frequency)等离子体激发过程简单可靠，具有很高的重复性，而且从本质上避免了高频激发电场的不均匀性，所形成的硅基薄膜致密均匀，且在合适的条件下能够形成微晶或纳米晶硅薄膜，极有利于以低成本的方式在大型真空镀膜设备中实施大面积薄膜的沉积。
附图说明
通过附图中所示的本发明的优选实施例的更具体说明，本发明的上述及其它目的、特征和优势将更加清晰。在全部附图中相同的附图标记指示相同的部分。并未刻意按比例绘制附图，重点在于示出本发明的主旨。在附图中，为清楚明了，放大了层的厚度。
图1为说明等离子体增强化学气相沉积工艺沉积薄膜方式的示意图；
图2至图6为说明根据本发明实施例的薄膜沉积方法的反应室剖面结构示意图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似推广。因此本发明不受下面公开的具体实施的限制。
本发明的薄膜沉积方法不同于普通的传统的PECVD工艺，传统的PECVD等离子体增强化学气相沉积工艺是利用射频辉光放电将原材料气体电离为等离子体，在基板表面沉积固态薄膜。本发明的薄膜沉积方法亦不同于包括溅射镀膜法(sputtering)和蒸发镀膜法(Evaporation)的物理气相沉积(Physical Vapor Deposition，PVD)法。溅射镀膜法是利用直流或高频电场使惰性气体(通常为氩)发生电离，产生辉光放电等离子体，电离产生的高能量正离子高速轰击靶材，使靶材上的原子或分子溅射出来，然后沉积到基板上形成薄膜。热蒸发或电子束蒸发依赖高温将沉积物质激活脱离蒸发源，而后沉积在相对低温的基板上。PVD物理镀膜法的原材料(‘靶材’或‘蒸发源’)的激活过程不依赖化学反应。
相比之下，本发明的薄膜沉积方法的核心概念是利用气态电离化学反应(刻蚀反应)以及在直流辉光放电时该反应的不对称性，将固态物质从阴极表面刻蚀剥离后扩散到阳极表面形成薄膜。以硅薄膜的沉积为例，在平行相对放置的阴极和阳极之间施加足够高的直流电压(电场)，利用直流辉光放电(直流等离子体激发)将刻蚀气体(氢气)激发为等离子体，刻蚀阴极表面的具有硅薄膜原材料(或硅片)的牺牲层，刻蚀剥离后的牺牲层物质(硅-氢原子团，Si-H radicals)再沉积到阳极表面的基板上形成含有硅-氢的薄膜。
直流辉光放电(dc glow-discharge)时，阴极(cathode，通常接直流电源的输出端)附近的等离子体密度要高于阳极(anode，通常为接地电极)附近的等离子体密度。所以，当具有刻蚀性的气体被直流电场激发为等离子体时，阴极表面要承受比阳极表面强烈得多的刻蚀。被刻蚀剥离的牺牲层材料的气相前驱体(precursors)扩散到阳极表面的基板上沉积，沉积回牺牲层的又很快被刻蚀掉。因此由直流电场中等离子体刻蚀的非对称性就产生了阳极表面基板上的薄膜沉积。换句话说，在适当的直流辉光放电条件下，刻蚀与再沉积是两个相互竞争的过程，当刻蚀气体为纯刻蚀原气体时，在阴极表面的刻蚀速率永远高于再沉积速率，在阳极表面则是再沉积的速率高于刻蚀速率，导致薄膜沉积。本发明的薄膜沉积方法本质上是一个依靠等离子体化学反应的物质转移方法。
下面结合图2至图6对本发明的薄膜沉积方法做详细的说明。首先如图2所示，本发明的薄膜的沉积方法首先在反应室100中放置第一电极板102和与之平行相对放置的第二电极板104，第一电极板102和第二电极板104之间的距离为1～10厘米，第一电极板102作为阳极，即正电极，第二电极板104作为阴极，即负电极。在第二电极板104的面向第一电极板102的表面具有牺牲层106，牺牲层106可以是采用任何方法沉积在第二电极板104表面的，将含有硅的气体混合物，例如硅烷与氢气的混合气体通入反应室，在任意选定的气压下，并在任意的温度下，使用任意的等离子体激发方式，包括直流、射频(RF)、极高频(VHF)、和甚高频(UHF)等。为了防止第一电极板102面对第二电极板104的表面也沉积上硅材料，可使用其他材料将其保护。或者利用假基板(dummy substrate)覆盖在第一电极板102面向第二电极板104的表面，沉积牺牲层106之后再将所述假基板移除。在本发明的其他实施例中，也可以在另一个反应室中先在第二电极板104表面沉积牺牲层106，然后再将具有牺牲层106的第二电极板104放置在反应室100中。牺牲层106作为后续沉积薄膜的原材料，其自身的材料即是沉积薄膜的主要原材料。例如，如果需要沉积氢化微晶硅(纳米晶硅)或非晶硅薄膜，那么牺牲层106就是以硅为主的材料，比如氢化硅薄膜。除了氢化硅之外，牺牲层的材料还可以是氢卤化硅(比如a-Si:H:F)、锗、氢化锗、氢化硅锗合金，其他半导体材料或各种相关的混合物，视所需沉积薄膜的情况而定。牺牲层106也可是贴附于第二电极板的薄板材料，比如硅晶圆(crystallinesilicon wafer)。
然后，在所述第一电极板102的面向牺牲层106的表面放置基板108，如图3所示，基板108需是导电材料，或表面镀有导电薄膜的材料，以使基板108与第一电极板102保持相同的电势。随后，通入刻蚀气体，刻蚀气体为氢气，还可以包括例如氩气(Ar)的惰性气体。在其他实施例中，刻蚀气体中还可以含有与牺牲层物质成分相同的元素，例如硅烷SiH4、SiF4或SiH2Cl2，此时若牺牲层厚度为零，也就是没有牺牲层的情况下，基板108表面并不会发生薄膜沉积。在其他实施例中，刻蚀气体中氢气的浓度大于50％，其余气体中至少有一种气体含有卤族元素，包括氟气F2，SiF4、SiH2Cl2、HF、HCl、Cl2、BF3、NF3、SF6中的一种或多种，以及惰性气体中的一种或多种。
在随后的工艺步骤中，将第一电极板102接地，向第二电极板104施加直流负电压，刻蚀气体被电离为等离子体对所述牺牲层106进行刻蚀，刻蚀剥离的物质扩散至基板108表面，在基板108表面沉积薄膜。上述直流负电压值为-150～-1000伏。
在其他实施例中，施加直流电场的同时，第一电极板102和第二电极板104还可分别施加一个或多个交变电场，或者第一电极板102和第二电极板104同时施加一个或多个交变电场。
在本发明的其他实施例中，在第一电极板102和第二电极板104之间还放置一个网状第三电极板(图中未示出)，在此情况下，第一电极板102、第二电极板103和该网状第三电极板可以分别或同时施加一个或多个交变电场。所述交变电场由包括低频、射频(RF)、极高频(VHF)的电源提供。
在通入刻蚀气体之前利用常规真空手段将反应室内的空气排出。在实施刻蚀导致的沉积过程中，反应室100内部的气体压力保持在1～10mbar(相当于100Pa～1000Pa)，比如2mbar(1.5torr，200Pa)，基板108的温度维持在100～260℃。通入刻蚀气体后，在直流电场的作用下，第一电极板102和第二电极板104之间的区域直流电场产生辉光放电，刻蚀气体被电离为等离子体，形成含氢H+的等离子体云110，如图4所示。被刻蚀而脱离出牺牲层106的硅材料在扩散的作用下不断向基板108方向移动，在第一电极板102和第二电极板104之间进行的直流辉光放电的大部分等离子体能量都被消耗在第二电极板104附近，而其对面的第一电极板102附近则具有相对很低的起刻蚀作用的等离子体(原子氢)密度，所以当刻蚀气体被直流电场激发为等离子体形成等离子体云110时，第二电极板104表面的牺牲层106所要承受的刻蚀作用要比第一电极板102基板108表面的强烈得多，虽然被刻蚀脱离牺牲层106的材料粒子和被刻蚀脱离基板108表面的材料粒子都会以较高的几率和速率再次沉积到牺牲层106和基板108表面，但是由于刻蚀作用的非对称性，再次沉积回牺牲层106的物质又迅速被刻蚀掉，而再次沉积回基板108表面的物质却有一部分或大部分被保留。因此，刻蚀作用的非对称性，即对刻蚀而言是牺牲层106大于基板108，所产生的净效果是在基板108表面原始粒子不断沉积形成薄膜112，而牺牲层106不断减薄，如图5所示。由刻蚀的非对称性所导致的沉积作用，通常所施加的直流放电功率越高，两个极板(牺牲层106表面到基板108表面)的间距越大、气压越高，在基板上沉积的速率越高，例如，可设置直流放电功率密度大于0.4W/cm2、反应区域气体压力大于1Torr，基板表面到牺牲层表面距离为2cm，两电极板的温度为100～250℃。
借助这种直流辉光放电所固有的等离子体刻蚀及再次沉积的非对称性，直流辉光放电所产生的氢离子对第二电极板104表面牺牲层106的刻蚀作用远远超过对第一电极板102的刻蚀作用，且刻蚀速率高于硅再沉积速率。随着刻蚀的继续，牺牲层106被刻蚀掉，在基板108表面因直流等离子体激发过程中刻蚀的非对称性形成薄膜112，如图6所示。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制。任何熟悉本领域的技术人员，在不脱离本发明技术方案范围情况下，都可利用上述揭示的方法和技术内容对本发明技术方案作出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化及修饰，均仍属于本发明技术方案的保护范围内。
Claims (10)
1、一种薄膜沉积方法，包括：
在反应室中平行放置作为阳极的第一电极板和作为阴极的第二电极板，在所述第二电极板面向所述第一电极板的表面具有牺牲层；
在所述第一电极板面向所述牺牲层的表面放置基板；
通入刻蚀气体；
将所述第一电极板接地，向第二电极板施加直流电压，将所述刻蚀气体电离为等离子体对所述牺牲层进行刻蚀，在所述基板表面沉积薄膜。
2、根据权利要求1所述的方法，其特征在于：所述直流电压值为-150伏～-1000伏。
3、根据权利要求1所述的方法，其特征在于：在所述第一电极板和第二电极板之间还放置网状第三电极板，在施加直流电场的同时，所述第一电极板和/或第二电极板和/或第三电极板上施加一个或多个交变电场。
4、根据权利要求3所述的方法，其特征在于：所述交变电场由包括低频、射频(RF)、极高频(VHF)的电源提供。
5、根据权利要求1所述的方法，其特征在于：所述刻蚀气体包括氢气H2。
6、根据权利要求5所述的方法，其特征在于：所述刻蚀气体中含有与牺牲层物质成分相同的元素，且当牺牲层厚度为零时，所述基板表面不发生薄膜沉积。
7、根据权利要求6所述的方法，其特征在于：所述刻蚀气体中氢气的浓度大于50％，其余气体中至少有一种气体含有卤族元素，包括氟气F2，SiF4、SiH2Cl2、HF、HCl、Cl2、BF3、NF3、SF6中的一种或多种，以及惰性气体中的一种或多种。
8、根据权利要求1所述的方法，其特征在于：所述第一电极板和所述第二电极板之间的距离为1厘米～10厘米。
9、根据权利要求1所述的方法，其特征在于：所述反应室内部的气体压力为1mbar～10mbar，基板的温度维持在100℃～260℃。
10、根据权利要求1所述的方法，其特征在于：所述牺牲层的材料为硅、氢化硅、锗、氢化锗、氢化硅锗合金或其他半导体材料，包括上述材料的卤化物合金。
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