CN101583737B - 无定形膜通过电子回旋共振的膜沉积 - Google Patents
无定形膜通过电子回旋共振的膜沉积 Download PDFInfo
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Abstract
公开一种通过从等离子体沉积而在衬底(14)上形成无定形材料膜、例如无定形硅膜的方法。将衬底放在具有限定容积的罩壳中,通过管子(20)将膜前体气体例如硅烷引入罩壳内。通过出口(22)从罩壳内抽出未反应的和离解的气体以便在罩壳内提供低压力。将微波能量引入罩壳内的气体中,从而通过分布式电子回旋共振在其中产生等离子体,并使材料从等离子体沉积至衬底上。定义为前体气体流量除以分布式等离子体源的面积的归一化前体气体流量大于或等于700sccm/m2,而且定义为反应器容积除以有效前体气体泵吸速率的气体停留时间不大于30ms。
Description
背景技术
本发明涉及通过从等离子体沉积至加工表面上而形成无定形材料膜的方法。更具体地,本发明涉及使用微波能量以通过电子回旋共振产生等离子体。特别关注的一个领域是在称为等离子体增强CVD(化学气相沉积)的工艺中,通过硅烷如SiH4、Si2H6或者更高阶低聚物的离解沉积无定形硅(a-Si:H)的膜。可以用于沉积无定形硅或无定形硅合金的其它前体气体包括其中硅与一个或多个碳、氧或氮结合、任选地连同氢一起存在的分子。硅合金的实例为SiOxNy所示类型的结构。此外,含硅气体可以与其它气体一起使用,例如锗烷、或可以用于沉积其它膜的不含硅的气体。关于无定形硅膜应用的特别关注的一个领域是将太阳能转化成电功率的装置。这类无定形硅材料还可以用于电子应用中,例如显示器用的TFT。本文使用的术语“无定形硅”表示氢化的无定形硅,a-Si:H。为了用于刚才提及的领域中,必须存在一些氢,通常是3-20%,以钝化作为缺陷的悬空键。
在激发等离子体至电子回旋共振(在下文缩写为“ECR”)的技术领域中,当静态或准静态磁场中电子的回转频率等于外加加速电场的频率时获得共振。对于磁场B,在由以下关系与B相关的激发频率f下获得该共振:
B=2πmf/e (1)
其中m和e是电子的质量和电荷。
当以电子回旋共振频率激发等离子体时,电子与电场同相旋转,并且连续地从满足ECR条件(1)的外部激发源获得能量从而达到离解或电离气体所必需的阈能。为了满足该条件,首先需要的是电子保持陷入磁力线,也就是它的回转半径相对于静态磁场梯度足够小,使得电子在它的回转期间看到基本上恒定的磁场,以及其次是回转频率相对于电子与中性成分例如原子和/或分子之间的碰撞频率保持较大。换句话说,当气体压力相对低且同时激发频率f高(这也意味着磁场强度B必须高)时,可望获得激发等离子体至电子回旋共振的最佳条件。
常规的发散ECR的主要困难在于,在大面积上产生密度基本上均匀的等离子体是不可能的。这意味着不能将它用于例如在大尺寸的加工表面上沉积基本上均匀的材料层。为了解决该问题,已经开发出一种称作分布式电子回旋共振(DECR)的技术,它使用其中多个等离子体激发装置形成网络的设备,这些装置共同地在加工表面产生密度基本上均匀的等离子体。单个的等离子体激发装置各自由微波能量的线式施加器构成,其一端与产生微波能量的源相连,相对一端安装有至少一个用于产生具有恒定且强度对应于电子回旋共振的磁场的至少一个表面的磁偶极子。该偶极子安装在微波施加器的端部,其安装方式确保加速到电子回旋共振的电子在极之间振荡,以至于产生位于远离施加器端部的偶极子一侧上的等离子体扩散区。各个激发装置相对于彼此分布并且位于加工表面附近,以便一起为加工表面产生均匀的等离子体。
上述DECR设备在美国专利6,407,359(对应于EP-1075168)中有描述,而且其中所述设备的更详细论述参照附图在下面给出。从那些图中可以清楚的是,从衬底看去,激发装置采取一般为矩形阵列的形式,其中包括该矩形为正方形的特定情况,因此有时将上述设备称为矩阵DECR(MDECR)设备。然而,应当理解的是,本发明还可以应用于如下的DECR设备,其中激发装置以非矩形的二维网络、例如六边形网络设置,或者其中存在装置的两条平行线,一条线中的装置相对于彼此偏移。六边形阵列的实例在以下给出:“Determination of theEEDF by Langmuir probe diagnostic in a plasma excited at ECRabove a multipolar magnetic field”,T.Lagarde,Y.Arnal,A.Lacoste,J.Pelletier,Plasma Sources Sci.Technol.10,181-190,2001。该装置还可以设置成环形、部分环形或近环形阵列。应当注意的是,在本发明人完成的一些工作中,已经用三个或六个装置围绕的中心等离子体激发装置进行沉积,周围装置的磁体极性与中心装置的磁体相反设置并且分别以三角形或六边形阵列设置。
此外,本发明可以应用于不是MDECR类型的DECR设备。因此,例如,它可适用于历史上在MDECR类型之前而且具有圆柱体形状并使用从该圆柱体的顶端延伸到底端的磁体和长天线的DECR反应器。上述设置在Michel Moisan和Jacques Pelletier的“Microwave ExcitedPlasmas”,Elsevier,1992中有描述,而且适合于均匀涂覆圆柱形衬底例如管子或者特征如下的物体:其尺寸(长度、半径)比等离子体双极平均自由程小(参见上述参考文献,附录9.1,第269-271页)。该物体可以具有位于等离子体的中心部分并垂直于圆柱体轴线定向的平坦表面。
我们惊讶地发现通过DECR工艺沉积的无定形硅膜的品质可以通过提高供入反应器内的气态前体的流量而改善。发现提高硅烷或其它前体气体的流量使材料带隙和膜中的氢含量减小,二者都是膜品质改善的标志。另外,膜的光电导率也增大,表明膜结构上的改善还伴随着缺陷密度的降低。当硅烷流量提高时,但是只有在短的气体停留时间下操作时,还观察到膜密度的提高。对于>30ms的如下定义的停留时间,当提高硅烷流量时没有观察到对膜密度的积极影响。
本发明最惊人的方面之一是对于供入DECR反应器内的微波功率的极其不同的值观察到膜品质的改善。在非常宽的微波功率范围内沉积高品质无定形硅膜。
我们还发现对于恒定的硅烷流量减少气体停留时间使膜的少数载流子扩散长度Ld(膜电子学品质改善的另一量度)增大,需要着重的是大的硅烷流量和短的气体停留时间的组合对于沉积同时具有光学和电子太阳能级性能的膜而言是重要的。另外应当提及为改善材料品质而提高硅烷流量导致更高的沉积速率。用于证明本发明的所有结果都是对以超过的速率沉积的膜测得。
总之,我们已经发现用于DECR反应器操作的新工艺体制,其导致在比用于太阳能级a-Si膜的现有技术沉积速率大得多的速率下具有改善的光学和电子性能的无定形硅膜的沉积。
发明内容
根据本发明,提供一种通过从等离子体沉积而在衬底上形成无定形材料膜的方法,该方法包括将衬底放在具有限定容积的罩壳中,将膜前体气体以一定流量连续引入罩壳内,从罩壳内抽出未反应的和离解的气体以便在罩壳内提供低压力,以及将微波能量引入罩壳内的气体中,从而通过分布式电子回旋共振(DECR)在其中产生等离子体并使材料从等离子体沉积至衬底上,其中定义为前体气体流量除以分布式等离子体源的面积的归一化的前体气体流量大于或等于700sccm/m2,而且定义为反应器容积除以有效前体气体泵吸速率的气体停留时间不大于30ms。
本文提到热电子约束区和热电子约束包络体。它们的定义如下。
热电子约束区是其中捕集热(快)一次电子的那些区域。这些是其中电子在相反极性的两个相邻磁极之间振荡的区域,这两个磁极可以是单一磁体的两极(以下称为“内磁极”)或两个相邻磁体的磁极(以下称为“间磁极”),其中满足绝热近似条件(相对于磁场梯度Larmor半径小),以及其中电子通过穿过满足ECR耦合条件的区域而获得能量。
磁体和热电子约束区限定出热电子约束包络体。这是磁体阵列包络体的容积,该包络体平行于磁体磁轴在两个方向上扩展并且扩展距离使得磁体间区域(如果有的话)延伸超过磁体末端,以及垂直于磁体磁轴在所有方向上扩展并且扩展距离使得磁体内区域延伸超过磁体的朝外表面。
附图说明
在下面参照附图进一步描述本发明,其中:
图1是显示如EP-1075168中描述和显示的等离子体产生设备的概略正视图,省去另外在图3a-3d中所示的引入和抽出气体的装置;
图2是图1设备的俯视图;
图3a-3d示出将气体引入该设备和从设备中抽出气体的四种可能方式;和
图4是显示材料带隙与归一化气体流量之间的关系的坐标图;
图5-7是显示三种其它性能与气体停留时间之间的关系和坐标图;和
图8a和8b显示了两种特定磁体构造的热电子约束包络体。
具体实施方式
图1和2显示相对于其上要沉积膜的衬底产生等离子体的设备。该设备包含概略表示并装配有进气装置和气体泵吸装置(图1中未示出)的密封罩壳1,它使得要电离或离解的气体的压力能够根据气体性质和激发频率保持在期望的值,该值例如可以是约10-2至2×10-1Pa。然而,可以使用小于10-2Pa(比如低至10-4Pa),或高于2×10-1Pa(比如高达5×10-1Pa,乃至1Pa或更大)的气体压力。例如,泵吸可以由1600l/s Alcatel Turbo-分子泵进行,它用来从罩壳中抽出气体。
使气体在质量流量控制器(MFC)的控制下从适当的气体源、例如压力气瓶进入罩壳。该气体例如可以包含SiH4作为膜前体气体,或者在上面关于无定形硅的沉积提及的其它气体中的一种。除了膜前体外,还可以引入诸如He、Ne或Ar的非反应性稀释气体,诸如氢、氮或氧的反应性气体,或诸如乙硼烷、三甲基硼或膦的掺杂剂气体。通常,任何这些其它气体通过与膜前体气体相同的端口、作为与它的混合物引入罩壳中,然而它们可以分别引入。供气***应当确保适当的气体流量进入反应器中,其通常为1-1000sccm(标准立方厘米/分钟)。
气体的注入口一般由***沉积室的单根管子或多根管子构成。该管子、或者存在多于一根的话则每根管子可以由格栅延伸,从而确保沉积室内气体的更均匀分布。可以在反应器中的任何地方进行注入,但是优选将膜前体气体引向衬底表面。用于本文时,应当理解提及设置出口以将气体引向衬底表面不仅包括其中使气体直接瞄准其上要沉积膜的衬底表面的情况,而且包括其中所述表面完全处于从出口在气流方向上延伸的线和与其成直角并穿过出口的线之间所限定的角度的情况。在上述情况下,从出口出来的气流将会具有朝着所述表面的所有部分的矢量分量。
一种称为“点”注入的进行注入的方法概略示于图3a中。在这种设置中,通过管子、或多根管子20(显示的是2根)引入膜前体,每根管子的出口21位于热电子约束包络体(由虚线近似表示)与衬底表面之间并且指向该表面。图3a还显示了出口22,通过它泵吸出未反应的和离解的气体。图3a的其它特征在下面参照图1所示的设备描述。其它特别感兴趣的注入设置为通过具有位于热电子约束包络体“内部”的出口31(图3c)或格栅40(图3d)的管30供给气体的设置。在图3d中气体离开的位置由箭头表示,应理解的是该格栅垂直于纸平面而且横向地延伸,以便存在遍布于整个热电子约束包络体上方的注入点。另一种称为“体积”注入的可能的注入设置示于图3b中。这里气体在与衬底和热电子约束包络体都显著隔开的位置或多个位置(显示的是两个)处进入沉积室。图3b显示这通过具有出口51的管50实现。这些和其它注入设置的优缺点论述于我们在与本申请相同日期提交并且题为“Method and apparatus for forming a film bydeposition from a plasma”和“Device for forming a film bydeposition from a plasma”的共同待决的申请中(我们的卷号G28331EP(欧洲专利申请No.06301115.9)和G28332EP(欧洲专利申请No.06301116.7))。
如上所述,图8a和8b显示了两种特定磁体构造的热电子约束包络体。在每张图中由粗线绘制的平行六面体表示该约束包络体。图8a示出整个多极构造的情况,其中每个磁体与它的居间近邻中的每一个都相反放置。图8b示出同极构造的情况,其中所有磁体相同取向。对于其它磁体构造,例如其中在给定行中的所有磁体具有相同取向、但是邻接行具有彼此相反取向的构造,可以构建合适的包络体。
等离子体室装配有衬底支架10,它显示为该设备的固定部件。衬底支架的一个作用是加热衬底至所需的沉积温度。这通常为室温与600℃之间,在沉积无定形硅的情况下优选超过200℃,更优选为225℃-350℃。这里提及的温度是实际的衬底温度,与可以通过测量衬底支架的温度而测得的标称衬底温度不同。该区别的重要性进一步论述于我们在与本申请相同日期提交并且题为“Method for forming a filmof amorphous silicon by deposition from a plasma”的共同待决的申请中(我们的卷号G27558EP(欧洲专利申请No.06301114.2))。
将其上具有至少一个衬底14、任选具有多个所述衬底的载板12可移动地安装在支架10上,以便可以将它与要涂覆的衬底一起带进室内,并在进行涂覆之后将其与衬底一起从室中取出。然而,作为替代可以用导热胶将衬底直接粘在衬底支架上。这改善衬底与衬底支架之间的热接触,否则在低压条件下难以实现该热接触。这进一步论述于我们在与本申请相同日期提交并且题为“Method for forming a filmof amorphous silicon by deposition from a plasma”的共同待决的申请中(我们的卷号G27558EP(欧洲专利申请No.06301114.2))。在这种情况下需要在沉积过程之前将支架与其衬底一起引入罩壳中并且事后从中取出。不用胶粘的话,一种设法改善衬底加热的方式是在低压膜沉积步骤之前存在其中用相对高压力(通常约100-200Pa)的气体填充罩壳的步骤。该高压气体提供跨越衬底与加热支架间可能存在的任何间隙的热传递,确保衬底的初始加热。另一种可能性是在衬底与衬底支架间放置导热碳膜。可以通过使热流体在衬底支架内循环而加热它,但是作为替代可以通过衬底支架中内嵌的电加热电阻器实现加热。然而,作为替代,可以直接加热衬底,例如通过使用红外灯加热。
衬底支架的另一个作用是容许衬底表面的极化以便控制朝向衬底的离子的能量。极化可以用RF电压源或用DC电压实现而且需要衬底支架对地电绝缘。通过将电绝缘的衬底支架与合适的RF或DC发生器16相连而实现极化,在RF极化的情况下使用合适的匹配电路。当在绝缘衬底上或在预先沉积于衬底(其可以是绝缘的或非绝缘的)上的绝缘层上沉积时,优选使用RF发生器。当在导电衬底或在预先沉积于导电衬底(可以导电或不导电)上的导电层上沉积时,可以通过与衬底表面具有合适电连接的RF或DC发生器施加偏压。在一种具体实施方案中,用经由自动调谐盒与衬底支架相连的13.56MHz Dressler发生器施加RF偏压。即使当使用RF发生器时,由于等离子体中的环境,衬底表面上所得的偏压也包含DC偏压分量。关于这如何发生的解释可以参见以下文献中完全不同的等离子体工艺的说明内容:Suzuki等人,“Radio-frequency biased microwave plasma etchingtechnique:A method to increase SiO2 etch rate”,J.Vac.Sci.Technol.B 3(4),1025-1033,七月/八月1985。
等离子体产生设备I具有一系列彼此隔开并位于衬底附近的独立等离子体激发装置3,从而一起运行以产生对于衬底均匀的等离子体。各个独立的等离子体激发装置3包含细长的微波能量施加器4。每个施加器4一端与各自的微波能量源相连,所述微波能量源位于罩壳1外部。然而,作为替代,单个微波能量源可以向所有的施加器4供给微波,或者可以存在数量上少于施加器数目的多个能量源。例如,一排十六个施加器可以方便地由两台2.45GHz微波发生器供给,该发生器各自具有2kW最大功率并且各自经由功率分配器和各自的铁芯调谐器供给八个施加器。每个施加器4有利地是被同轴管4’环绕的管形式,从而使得微波能量能够传播到其自由端同时避免辐射微波,和减少施加器之间的微波耦合。为了确保微波能量适当传递到等离子体中,每个施加器优选配备使反射功率减到最少或至少减小该反射功率的匹配装置。
每个微波施加器4的自由端与至少一个永磁体5相连。每个磁体的磁轴(优选)与磁体本身的长轴平行。在这种设置的一种特定形式中,所有等离子体激发装置的磁体在相同方向上定向(单极构造),也就是它们所有的北极在顶部且它们所有的南极在底部,反之亦然。在另一形式中,各极中的一些在顶部以及各极中的一些在底部(多极构造)。后者的一个实例为如下阵列,如图2从一端观看并且沿着装置的任何给定的行或列,相继遇到交替极性的极。另一实例为给定行(或列)中的所有磁体具有相同极性,但是列(或行)具有交替极性。然而,还可以使用其中磁体的磁轴并不平行于磁体本身的长轴的设置,只要存在磁场的磁力线平行于微波传播矢量的显著区域即可。为了确保存在其中可以发生ECR衰减的显著区域,这是必要的。
如上所述,本发明基于对前体气体流量和气体停留时间在实现沉积膜的某些可导出性能方面的重要性的认识。现在基于为形成无定形硅膜而用SiH4作为前体气体进行的25个DECR膜沉积实施例的实验结果(在表1和2中列出),更详细描述这些因素的影响。除了所得产物要进行红外分析的情形(在该情形中在硅晶片上沉积)外,在Corning 1737玻璃上沉积所述膜。为了分析简单起见,进行这些实施例时没有使用另外的气体。在每一沉积过程中,将多个衬底安置在衬底支架上且它们之间具有间隙。罩壳容积为25.5升。作为在水平面内形成磁体包络体的线所围住的面积的分布式等离子体源的面积为702cm2,即0.0702m2。表1和2中所用的标题具有下列含义:
注入:所使用的注入类型,即点或管。
SiH4/m2(sccm/m2):通过除以分布式等离子体源的面积、即0.0702m2而归一化的按每分钟标准cm3计的硅烷流量(SiH4的引入速率)。
停留时间:前体气体在罩壳中的停留时间,按ms计。停留时间的定义在下面更详细说明。
MW/gas(W/sccm):通过除以按每分钟标准cm3计的硅烷流量而归一化的微波功率(W)。
RF偏压(伏):向衬底施加的偏压,即通过使用外加RF电压获得的DC偏压。
温度(C):按℃计的衬底标称温度。对于实施例18-24,它精确地表示表面温度。对于实施例1-17,它是衬底支架温度,而衬底表面温度可能为50-75℃,由于热接触不良而低于衬底支架温度。
P气体(mTorr):按mTorr计的罩壳内的气体压力(1mTorr=0.1333Pa)。
P等离子体(mTorr):存在等离子体时的按mTorr计的气体压力。
d:按计的沉积膜厚度,其按照如下文献所述的方法由椭偏光谱法测定:A.Fontcuberta i Morral,P.Roca i Cabarrocas,C.Clerc,“Structure and hydrogen content of polymorphoussilicon thin films studied by spectroscopic ellipsometry andnuclear measurements”,PHYSICAL REVIEW B 69,125307/1-10,2004。
εi(max):膜介电常数ε的模型化虚部的最大值εi(max),它与材料密度紧密联系,其中密度变化归因于空隙体积的变化(由于εi随波长变化而提出最大值,而且最大值可以在各种不同的波长下产生)并按照上面提及的方法用Tauc-Lorentz模型由椭偏光谱法测定。
Eg(eV):按eV计的材料带隙,按照上面提及的方法由椭偏光谱法测定。
C:按照上面提及的方法由椭偏光谱法测定的膜材料的矩阵无序系数。
Ld(nm):按nm计的少数载流子扩散长度。
IF0:照度系数,它是膜的光电导率与暗电导率之间的比率。
∑光电导率(1/ohm.cm):按(ohm.cm)-1计的在未校准但是恒定的白光照射下测定的膜光电导率。
使用多种表征技术来评价产生的无定形硅膜的光学和电子学品质。
通过椭偏光谱法在1.5-4eV的能量范围内测定光学性能,其容许评价:
●膜的光学带隙
○对于光伏应用需要小的带隙,因为它意味着更宽波长范围内的入射光的吸收。
○通常小的带隙还与低的膜氢含量有关,它对膜稳定性具有正面影响。
●介电常数虚部的最大值。
○该性能是膜密度的间接测量。更高的值表示更致密的膜。
●膜厚度以及由此的沉积速率。
○在当前的操作条件下,等离子体在高MW功率下运行在硅烷损耗模式中,沉积速率与硅烷流量成正比例。
从电导率测量结果推导膜的电子性能。
●膜光电导率,在膜表面上在两个共面电极之间测量。
○它是偏压下膜电子学品质的量度。
○通常更好的材料在照射下显示出更大的电导率,但是通过大的电场可以消除电荷陷阱的影响。
●照度系数(IF0),它是光电导率与暗电导率之间的比率。
○对于无定形材料,该值越高,材料越好。
○在当前情形中在该层退火之前对其进行测量并且因此更多地存在在退火时可能消失的缺陷。
●通过SSPG(稳态光载流子光栅)测定少数载流子(空穴)扩散长度。
○它在于用分成2束的极化激光束照射试样。2束光束当极化平行时在样品中干涉产生干涉光栅,并且当极化垂直时均匀照射。
○当改变光栅周期和入射角度时,从“干涉”和“均匀”照射光电导率之比推导出双极扩散长度。
表1
实施例 | 注入 | SiH4/m2 | 停留时间 | MW/gas | RF偏压 | 温度 | RF功率 | P气体 | P等离子体 |
sccm/m2 | ms | W/sccm | 伏特 | C | W | mTorr | mTorr | ||
1 | 点 | 712 | 30.80 | 60.00 | -114 | 225 | 300 | 0.77 | 5.56 |
2 | 点 | 712 | 21.44 | 60.00 | -57 | 225 | 0.53 | 1.82 | |
3 | 点 | 712 | 21.04 | 20.00 | -114 | 225 | 170 | 0.52 | 1.74 |
4 | 点 | 712 | 32.41 | 20.00 | -57 | 225 | 0.81 | 5.36 | |
5 | 点 | 2136 | 21.10 | 20.00 | -114 | 225 | 1.57 | 9.57 | |
6 | 点 | 2136 | 31.61 | 20.00 | -57 | 225 | 2.36 | 30.72 | |
7 | 点 | 2136 | 21.37 | 6.67 | -57 | 225 | 1.59 | 8.04 | |
8 | 点 | 2136 | 21.24 | 6.67 | -57 | 225 | 1.58 | 8.79 | |
9 | 点 | 2136 | 31.61 | 6.67 | -114 | 225 | 2.36 | 24.91 | |
10 | 点 | 2848 | 24.76 | 5.00 | -100 | 225 | 2.46 | 15.04 |
11 | 点 | 2136 | 36.51 | 6.67 | -100 | 225 | 2.72 | 37.04 | |
12 | 点 | 2136 | 25.37 | 4.67 | -100 | 225 | 1.89 | 8.88 | |
13 | 点 | 2848 | 28.70 | 3.50 | -100 | 225 | 2.85 | 24.44 | |
14 | 点 | 2848 | 28.70 | 3.50 | -76 | 225 | 2.85 | 24.44 | |
15 | 点 | 2848 | 28.70 | 3.50 | -57 | 225 | 2.85 | 24.44 | |
16 | 点 | 2848 | 28.70 | 3.50 | -38 | 225 | 2.85 | 24.44 | |
17 | 点 | 2848 | 28.70 | 3.50 | -19 | 225 | 2.85 | 24.44 | |
18 | 管 | 1495 | 27.61 | 19.05 | -25 | 225 | 44 | 1.44 | 6.13 |
19 | 管 | 1495 | 27.80 | 19.05 | -25 | 225 | 37 | 1.45 | 6.17 |
20 | 管 | 1495 | 29.72 | 19.05 | -25 | 225 | 31 | 1.55 | 10.39 |
21 | 管 | 1495 | 33.74 | 19.05 | -25 | 225 | 21 | 1.76 | 18.96 |
22 | 管 | 1495 | 34.56 | 19.05 | -25 | 225 | 19 | 1.80 | 20.76 |
23 | 管 | 1495 | 27.61 | 19.05 | -25 | 275 | 44 | 1.44 | 6.13 |
24 | 管 | 1495 | 30.29 | 19.05 | -25 | 275 | 35 | 1.58 | 10.64 |
25 | 管 | 1495 | 33.94 | 19.05 | -25 | 275 | 25 | 1.77 | 19.13 |
表2
如上所述,本发明基于的发现之一是某些改善与短的前体气体停留时间有关。就本发明而言,给定DECR反应器的气体停留时间定义为按升计的反应器罩壳体积除以按升/秒计的真空泵运行时的有效泵吸速率。有效泵吸速率是实际从反应器中抽出气体的速率。由于等离子体/沉积室和涡轮分子泵之间的连接管的存在,真空泵将会由于管道所产生的传导性的变化而实际在低于其额定值(即它在泵入口处的泵吸速率)的速率下泵吸。表1和2中给出的实施例来自于如上所述体积为25.5升的反应器。
下面参照显示发现多种膜性能如何根据气体流量和/或气体停留时间变化的图论述获得的结果。首先将单独考虑这些特征各自的影响,然后组合考虑。
已经发现提高硅烷流量,并因此提高沉积速率,对材料带隙具有重大影响,带隙在流量增大时减小。通过着眼于在增大的流量下制成的相同厚度的膜,并且观察到流量越高所得的膜越暗,也清楚地看到这一点。图4显示更高的流量导致显著更小的带隙。
因此,基于上述品质准则,为了获得适合用于薄膜太阳能电池的材料带隙,面积归一化的硅烷流量应当尽可能高而且无论如何应当超过700sccm/m2。优选地流量应当至少是1000sccm/m2,更优选至少1500sccm/m2,再优选至少2000sccm/m2,和更加优选至少2500sccm/m2。然而,相对于这一标准没有上限,尽管在与停留时间上的要求(在下面论述)结合时由硬件或经济限制产生上限。
气体停留时间
材料密度
经由膜介电常数的虚部最大值(εi(max))测量膜密度。如图5所示,在减少气体停留时间的情况下,εi(max)以及由此膜密度增大。温度也有影响,因为升高衬底温度趋于使材料致密。然而在研究的范围内,气体停留时间起主要作用而且短的气体停留时间是非常优选的从而实现最高的可能材料密度。
硅烷流量对介电常数的影响小,但是对于影响大得多的其它品质参数将对此进一步论述。着眼于实现太阳能用途的最低准则,气体停留时间应当不超过30ms以满足εi(max)准则。
电荷输送性能
通过着眼于电荷输送性能,例如少数载流子扩散长度(Ld),或者比较光电导率与暗电导率(称为照度系数,IF0),可以评价材料的电学性能。在两种情况下,这些性能本质上受气体停留时间影响,如同从图6和7中可以看出的那样。
在本文中不用达到特定的照度系数以得出制备膜的方法的标准。这是由于尽管更大的照度系数表示更好的材料品质,但是在特定照度系数的达到与特定品质的材料的获得之间没有相关性。然而,已经发现减少硅烷气体停留时间正面影响照度系数。
另一方面,确定少数载流子扩散长度应当大于100nm。基于提供的数据,发现气体停留时间应当不超过30ms以实现该目标。
总之,基于通过DECR沉积的aSi:H层的形态、光学、电学和电荷输送性能,气体停留时间应当不超过30ms以达到对于在薄膜太阳能电池中的应用足够好的材料品质。优选地,它应当小于28ms,更优选小于25ms,再优选小于22ms。
气体停留时间与面积归一化气体流量的组合
对于上述性能,面积归一化的气体流量和气体停留时间没有显示出交叉相互作用。这意味着各自可以独立地设定以实现良好的材料品质。然而,已经发现对于所有性能而言并非如此而且若干性能以相互关联的方式取决于前体气体流量和前体气体停留时间两者。对于表面粗糙度和矩阵无序参数是这种情况。
表面粗糙度本身不是制造太阳能电池的品质标准。然而,经验法则是粗糙的膜无法容许制造良好的薄膜太阳能电池。当最后沉积的层是窗口层时尤为如此,因为它需要非常薄而且在沉积膜上形成保形层。不能形成保形层造成薄膜太阳能电池内的电场的分流和不均匀性,这显著影响电池转换效率。因此安排工艺条件以使得材料粗糙度减到最小。如果窗口层通过低密度/低压等离子体工艺例如磁控管溅射沉积,这将会是特别有效的。
如同从表1和2中可以看出的那样,表面粗糙度受硅烷流量/气体停留时间的组合以及受衬底偏压影响。表中的数据显示为了实现低表面粗糙度,停留时间应当尽可能短而且流量应当尽可能高。对于期望实现低水平的值的矩阵无序参数C,观察到相同类型的趋势。
Claims (16)
1.一种通过从等离子体沉积而在衬底上形成氢化无定形硅膜的方法,该方法包括将衬底放在具有限定容积的罩壳中,将膜前体气体以一定流量连续引入罩壳内,从罩壳内抽出未反应的和离解的气体以便在罩壳内提供低压力,以及将微波能量引入罩壳内的气体中,从而通过分布式电子回旋共振在其中产生等离子体并使材料从等离子体沉积至衬底上,其中定义为前体气体流量除以分布式等离子体源的面积的归一化前体气体流量大于或等于700sccm/m2,而且定义为反应器容积除以有效前体气体泵吸速率的气体停留时间不大于30ms。
2.权利要求1的方法,其中所述膜前体气体包含硅烷。
3.权利要求2的方法,其中所述膜前体气体包含SiH4。
4.前述权利要求任一项的方法,其中通过设置形成二维网络的装置产生等离子体。
5.权利要求4的方法,其中通过矩阵分布式电子回旋共振产生等离子体。
6.权利要求1的方法,其中罩壳内的压力为10-4Pa至1Pa。
7.权利要求6的方法,其中所述压力为至少10-2Pa。
8.权利要求6或7的方法,其中所述压力不超过2×10-1Pa。
9.权利要求1的方法,其中通过RF发生器向衬底赋予DC电压偏压。
10.权利要求1的方法,其中所述归一化的前体气体流量是至少1000sccm/m2。
11.权利要求1的方法,其中所述归一化的前体气体流量是至少1500sccm/m2。
12.权利要求1的方法,其中所述归一化的前体气体流量是至少2000sccm/m2。
13.权利要求1的方法,其中所述归一化的前体气体流量是至少2500sccm/m2。
14.权利要求1的方法,其中所述气体停留时间小于28ms。
15.权利要求1的方法,其中所述气体停留时间小于25ms。
16.权利要求1的方法,其中所述气体停留时间小于22ms。
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