CN101851742A - 一种化合物半导体薄膜的制备方法 - Google Patents

一种化合物半导体薄膜的制备方法 Download PDF

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CN101851742A
CN101851742A CN200910106258.9A CN200910106258A CN101851742A CN 101851742 A CN101851742 A CN 101851742A CN 200910106258 A CN200910106258 A CN 200910106258A CN 101851742 A CN101851742 A CN 101851742A
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substrate
preparation
evaporation
evaporation source
compound semiconductor
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CN101851742B (zh
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钟北军
曹文玉
周勇
姜占锋
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BYD Co Ltd
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Priority to PCT/CN2010/071333 priority patent/WO2010111927A1/en
Priority to US13/258,174 priority patent/US8470692B2/en
Priority to EP10758029.2A priority patent/EP2414556A4/en
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Abstract

本发明属于太阳能电池技术领域。本发明提供了一种化合物半导体薄膜的制备方法，其包括：在真空条件下，加热蒸发源中的源材料，使其蒸镀到基片上；所述基片绕其几何中心，在所述基片所在的平面内旋转，所述基片相对水平面倾斜。本发明所提供制备方法制出的化合物半导体薄膜厚度均匀性好，且薄膜面积大；并且工艺简单高效、容易实现，同时本发明能够直接适用于工业生产，具有巨大的商业价值。

Description

一种化合物半导体薄膜的制备方法
技术领域
本发明属于太阳能电池技术领域，特别是涉及太阳能电池中化合物半导体薄膜的制备方法。
背景技术
化合物半导体薄膜系列太阳能电池是各种薄膜太阳能电池中效率最高、最有发展前途的薄膜太阳电池之一，化合物半导体材料由于是已知的半导体材料中光吸收系数最高的，最高达到105/cm；并且没有光致衰退效应的半导体，此外光照甚至会提高其转换效率，因此此类太阳能电池的工作寿命长。有实验结果说明化合物半导体薄膜太阳能电池寿命比寿命较长的单晶硅电池的寿命(一般为40年)还长。而且化合物半导体是直接带隙的半导体材料，最适合薄膜化。
目前制备化合物薄膜半导体方法很多，为了克服现有方法的缺陷，出现了真空蒸发镀膜法。
真空蒸发镀膜法是指在真空条件下，加热蒸发容器中源材料，使其原子或分子从表面气化逸出，形成蒸汽流，入射到基片表面，凝结成固态薄膜。采用此法制备的化合物半导体薄膜太阳电池，转化效率高，但是所制备电池面积远小于1cm2，这主要是受蒸发源的发射特性的限制，在制备大面积薄膜时，镀料分布不均匀现象严重，面积愈大不均匀表现愈突出。由于太阳电池要求的面积较大，因此不具有商业应用价值。
为了改进该方法，有人采用基片直线运动，并通过棒状蒸发源蒸发镀膜，这样虽然能够在一定程度上制备较大面积的半导体薄膜，但是其均匀程度还是较低，一般在±10％左右，并且棒状蒸发源很难制备，这是用于为了使蒸发源能够均匀蒸发，必须是棒状蒸发源在蒸发的过程中各个位置温度相同，不存在任何的位置出现过慢或者过快蒸发，甚至蒸发源内部的缺陷分布也会影响蒸发源，使蒸发源某些位置出现过快或者过慢蒸发，因此棒状蒸发源在理论上需要复杂的计算，在工艺加工上也非常困难；整套设备控制精密及价格昂贵。
发明内容
本发明所要解决的技术问题是：现有真空蒸发镀膜法，蒸发源难加工，薄膜不均匀的现象。
本发明提供了一种简单方便、蒸镀均匀的真空蒸镀方法。
一种化合物半导体薄膜的制备方法，其包括：
在真空条件下，加热蒸发源中的源材料，使其蒸镀到基片上；所述基片绕其几何中心，在所述基片所在的平面内旋转，所述基片相对水平面倾斜。
本发明所提供制备方法制出的化合物半导体薄膜厚度均匀性好，且薄膜面积大；并且工艺简单高效、容易实现，同时本发明能够直接适用于工业生产，具有巨大的商业价值。此外本发明可以在原有蒸镀设备上直接改装实施，且改装容易，投入也较低，能够实现较小的设备制备较大尺寸的基片，在实际生产中更具有可实施性。
具体实施方式
一种化合物半导体薄膜的制备方法，其包括：
在真空条件下，加热蒸发源中的源材料，使其蒸镀到基片上；所述基片绕其几何中心，在所述基片所在的平面内旋转，所述基片相对水平面倾斜。
所述化合物半导体薄膜为本领域技术人所公知的，例如CIS薄膜、CIGS薄膜、CuInS2薄膜、CIGSS薄膜、CdS薄膜、CdTe薄膜等。
所述真空条件为本领域技术人员所公知的，一般是指3.0×10-3Pa以下。本发明该优选对蒸镀系统进行烘烤，进一步提高真空度。
所述源材料为本领域技术人所公知，一般为根据所要制得的化合物半导体薄膜选取相应的金属单质或者合金的粉末状固体，例如制备铜铟镓硒半导体薄膜所用的源材料可以为Cu、In、Ga和Se；也可以是CuSe合金、InSe合金、GaSe合金；或者直接使用铜铟镓硒作源材料等。还例如制备CdTe半导体薄膜，可以选取Cd粉和Te粉，也可以选取CdTe作源材料。
所述蒸发源为本领域技术人员所公知的，为源材料的加热蒸发容器，将上述源材料置入蒸发源中，加热蒸发源，源材料受热蒸发。蒸发源按其加热方式的不同有电阻蒸发源、电子束蒸发源、高频感应蒸发源、激光束蒸发源等。
所述基片亦为本领域技术人员所公知的，一般为正方形，材料可以选自各种玻璃和高分子有机物制备的柔性基片，而本发明工艺所使用的基片为普通钠钙玻片上磁控溅射一层1μm的Mo电极层基片。
所述基片在使用前需经过超声波清洗，以保证基片洁净。
所述蒸发源根据所述源材料的选取的不同，可以设置一个或者多个。若直接选取铜铟镓硒作源材料，即可设置一个蒸发源。若选取Cu、In、Ga和Se作为源材料，就分别设置Cu蒸发源、In蒸发源、Ga蒸发源和Se蒸发源四个蒸发源。
所述蒸镀为本领域技术人员所公知的。
本发明具体的步骤如下：
首先将经过超声波清洗的基片倾斜固定在蒸发源的正上方，向各蒸发源中铺入源材料；然后将体系抽真空，加热基片加热到300-600℃并恒温保持，加热蒸发源，并逐渐调整各个蒸发源的蒸镀速度；调整基片旋转速度，打开挡板，开始蒸镀；蒸镀结束后，关闭挡板，继续给基片加热一段时间，使化合物半导体薄膜反应更充分；然后基片自然冷却到常温，关闭抽真空系统并向体系中内缓慢充入保护气。在体系内气压达到大气压时，将基片取出，基片上就蒸镀上了一层化合物半导体薄膜。
所述基片的旋转速度优选为3-100r/min。
所述基片与水平面的夹角优选为5-30度。更优选为7-8度。
本发明所述与水平面的夹角指锐角夹角。
若为多个蒸发源，本发明还优选多个蒸发源位于同一水平圆的圆周等分点上。
所述基片的几何中心位于所述水平圆的圆心处的垂线上。
所述水平圆的半径优选为基片边长的8～10倍。
这样，由于蒸发源的均匀分布，基片在旋转过程中可以实现多种元素的同时蒸镀，并根据蒸发源蒸发的蒸发流分布特点，使基片倾斜一定的角度，这样基片上薄膜的厚度可以实现一定的补偿作用，因此这样制备的薄膜化学成分均匀性更好，并且在较大面积上可以实现均匀镀膜。
一般控制各蒸发源的蒸镀速率在0.3-16nm/min。
所述保护气为本领域技术人员所公知的，一般为高纯氩气或者氮气。
本发明制出的化合物半导体薄膜，按照其边长三等分将其均匀分成形状相同9个区域，之后测量该整片薄膜的均匀性，测试结果表明薄膜厚度的均匀性均在±5％以内；而使用现有蒸镀法制备相当面积基片的薄膜均匀性一般在±17.5％，最好的也只能能够达到±10％。
本发明制出的化合物半导体薄膜，各元素比例分布均匀，能够较好的控制较大面积上薄膜的成分，用EDS分析基片各区域的各组成元素比例，其结果说明基片各个区域成分几乎相同，本发明特别适合于制备对成分比例控制要求严格的化合物半导体薄膜材料，如多晶薄膜太阳电池CIS层、CIGS层、CuInS2层、CIGSS层、CdS、CdTe等。
本发明制出的化合物半导体薄膜具有优良的光电性能，制备的CIGS太阳电池(电池尺寸15×15cm2)在AM1.5光强条件下测试，其最高电池转换效率达到14.93％，已经具有商业生产价值。
本发明继承了真空蒸发工艺的优点，可以很好的控制薄膜的晶体质量和电学性质，并且工艺简单高效、容易实现，此外本发明可以在原有蒸镀设备上直接改装，且改装容易，投入也较低，能够实现较小的设备制备较大尺寸的基片(15×15cm2)，在实际生产中更具有可实施性。
以下结合具体实施例对本发明作进一步的阐述。
实施例1
(1)将经过超声波清洗的基片，牢固夹持在基片夹具上，使基片与水平面的夹角为8度。所述基片为15×15cm2的普通钠钙玻璃上磁控溅射一层1μm的Mo电极层基片。
(2)将分别盛有Cu、In、Ga和Se的蒸发源均匀固定在同一水平圆周上，即将水平圆周四等分，四个蒸发圆位于四个等分点上。所述水平圆周的半径为基片边长的9.0倍。
(3)将体系抽真空到3.0×10-3Pa，之后对整个蒸镀系统进行烘烤除气，进一步提高真空度到2.0×10-4Pa，同时加热基片到500℃并保持该温度。
(4)调整各个蒸发源到一定的蒸镀速度，Cu蒸发源的蒸镀速度为15nm/min，In蒸发源的蒸镀速度为12nm/min、Ga蒸发源的蒸镀速度为7nm/min、Se蒸发源的蒸镀速度为35nm/min。
(5)调整基片旋转转速，设定基片旋转转速5rad/min。在调整好各个设定的参数后打开各个蒸发源的蒸发挡板开始蒸镀，蒸镀50min，达到蒸镀时间后关闭蒸发挡板，继续加热3分钟之后停止基片加热，待基片自然冷却到常温；
(6)最后，关闭抽真空系统并向真空腔内缓慢充入高纯氮气使真空腔内气压达到大气压，将基片取出，在基片上就蒸镀上了一层薄膜。产品记作A1。
实施例2
与实施例1所不同的是，基片与水平面的夹角为5度。所述水平圆周的半径为基片长边长的8.0倍，基片旋转转速20rad/min，其他部分同实施例1。产品记作A2。
实施例3
与实施例1所不同的是，基片与水平面的夹角为30度，所述水平圆周的半径为基片长边长的10倍，基片旋转转速90rad/min。其他部分同实施例1。产品记作A3。
实施例4
本实施例制备工艺与实施例1基本相同，只是将基片改换成CBD沉积法沉积一层CdS层的基片，此外将蒸发源材料换成金属Cd和Te，并且其蒸发速率调整为32nm/分和47nm/分，转速调整为90转每分，蒸镀时间为33分钟；其他部分同实施例1。产品记作A4。
实施例5
与实施例4所不同的是，设定基片旋转转速5rad/min，倾角调整到30度。其他部分同实施例4。产品记作A5。
对比例1
与实施例1所不同的是，所述基片不倾斜，于水平面无夹角。其他部分同实施例1。产品记作D1。
对比例2
与实施例1所不同的是，所述基片倾斜35度，即于水平面的夹角为35度。其他部分同实施例1。产品记作D2。
对比例3
与实施例4所不同的是，所述基片倾斜35度，即于水平面的夹角为35度。其他部分同实施例4。产品记作D3。
性能测试：
薄膜厚度均匀性
将薄膜A1-A5以及D1-D3按照图1分区，分别用Xp-2台阶仪测定各个分区薄膜厚度。其厚度分别记作x1、x2、x3、x4、x5、x6、x7、x8、x9。其平均数为x0，本发明选用(xi-x0)/x0(i＝1～9)的最大值和最小值，来评价薄膜厚度均匀性。
光转换效率
光电转换效率的测量是通过首先测量电池的J-V特性，然后计算出来的，电池的J-V特性的测试是在实验室太阳光模拟器(AM1.5)下进行的，采用氙灯作为光源。模拟器的光强采用天津电子18所205计量站提供的单晶Si标准电池进行校准，调节模拟器光源的输出功率，使标准电池的短路电流达到标定值，电池的测试温度为25℃。
薄膜化学成分均匀性
薄膜化学成分均匀性是将薄膜A1-A5以及D1-D3按照图1分区，分别用美国NORAN公司QUEST型X-射线能谱仪测定各个分区薄膜的原子比值。其原子比值分别记作y1、y2、y3、y4、y5、y6、y7、y8、y9。其平均数为y0，本发明选用(yi-y0)/y0(i＝1～9)的最大值和最小值，来评价薄膜成分均匀性。
表1
  实施例   厚度均匀性   光转换效率
  A1   ±1.2％   14.939％
  A2   ±3.17％   10.930％
  A3   ±2.56％   11.341％
  D1   -8.36％～8.07％   2.419％
  D2   -9.07％～7.56％   2.851％
表2
  实施例   厚度均匀性   化学成分均匀性
  A4   ±2.8％   -1.35％～2.8％
  A5   ±4.7％   -3.98％～4.77％
  D3   -9.65％～8.07％   -11.3％～35.8％
从表1可以看出本发明在制备铜铟镓锡时，通过实施例和对比例比较，薄膜厚度的均匀性有了明显的提高。而且其光转化效率也有较大幅度提高。
从表2可以看出本发明在制备硫化镉时，通过实施例和对比例比较，薄膜厚度的均匀性有了明显的提高。而且薄膜化学成分均匀性有了一定提高。

Claims (10)

1.一种化合物半导体薄膜的制备方法，其包括：在真空条件下，加热蒸发源中的源材料，使其蒸镀到基片上；其特征在于：所述基片绕其几何中心，在所述基片所在的平面内旋转，所述基片相对水平面倾斜。
2.根据权利要求1所述的制备方法，其特征在于：所述基片与水平面的夹角为5-30度。
3.根据权利要求2所述的制备方法，其特征在于：所述基片与水平面的夹角为7-8度。
4.根据权利要求1所述的制备方法，其特征在于：所述基片的旋转速度为3-100r/min。
5.根据权利要求1所述的制备方法，其特征在于：所述蒸发源的个数为至少两个，所述蒸发源位于同一水平圆的圆周等分点上。
6.根据权利要求5所述的制备方法，其特征在于：所述基片为正方形，所述水平圆的半径为基片的边长的8～10倍。
7.根据权利要求5所述的制备方法，其特征在于：所述基片的几何中心位于所述水平圆的圆心处的垂线上。
8.根据权利要求1所述的制备方法，其特征在于：所述蒸发源的蒸发速度为0.3-16nm/min。
9.根据权利要求1所述的制备方法，其特征在于：所述蒸镀的时间为30-60min。
10.根据权利要求1所述的制备方法，其特征在于：蒸镀时，所述基片的温度为300-600℃。
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