CN102598299A - 太阳能电池及其制造方法 - Google Patents

太阳能电池及其制造方法 Download PDF

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CN102598299A
CN102598299A CN2010800492881A CN201080049288A CN102598299A CN 102598299 A CN102598299 A CN 102598299A CN 2010800492881 A CN2010800492881 A CN 2010800492881A CN 201080049288 A CN201080049288 A CN 201080049288A CN 102598299 A CN102598299 A CN 102598299A
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李东根
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LG Innotek Co Ltd
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Abstract

根据本发明的太阳能电池包括：图案层，布置在衬底上且包括不平整图案；后电极，布置在所述图案层上；光吸收层，布置在所述后电极上；缓冲层，布置在所述光吸收层上；以及前电极，布置在所述缓冲层上。根据本发明的太阳能电池制造方法包括：在衬底上形成包括不平整图案的图案层；在所述图案层上形成后电极；在所述后电极上形成光吸收层；在所述光吸收层上形成缓冲层；以及在所述缓冲层上形成前电极。

Description

太阳能电池及其制造方法
技术领域
本发明涉及一种太阳能电池及其制造方法。
背景技术
近来，随着能量需求的增长，正在对将太阳能转化为电能的太阳能电池进行研究。
具体地，已广泛使用基于CIGS的电池，所述基于CIGS的电池是pn异质结设备，具有包括衬底、金属后电极层、p型基于CIGS的光吸收层、高电阻缓冲层、n型透明电极层等的衬底结构。
各种类型的衬底都可以用作所述衬底，但是当衬底是挠性的时，在衬底被弯曲的情况下，导致在衬底上形成的金属后电极层中产生裂缝的问题。
发明内容
技术问题
本发明一些方面的优点在于，提供一种太阳能电池及其制造方法，所述太阳能电池能够增加衬底和后电极之间的联结力。
技术方案
根据本发明的太阳能电池包括：图案层，布置在衬底上且包括不平整图案；后电极，布置在所述图案层上；光吸收层，布置在所述后电极上；缓冲层，布置在所述光吸收层上；以及前电极，布置在所述缓冲层上。
根据本发明的太阳能电池制造方法包括：在衬底上形成包括不平整图案的图案层；在所述图案层上形成后电极；在所述后电极上形成光吸收层；在所述光吸收层上形成缓冲层；以及在所述缓冲层上形成前电极。
有益效果
根据实施例的太阳能电池及其制造方法可以在衬底上形成纳米尺寸的不平整图案，由此提高与形成在衬底上的后电极的联结力。
具体地，当衬底是挠性的时，尽管衬底被弯曲，但是不会在衬底和后电极之间产生裂缝。
就是说，后电极还形成在不平整结构图案的凹槽内部，以增加衬底和后电极之间的联结力。
此外，光吸收层(其一部分与衬底相接触)也与不平整结构图案接触，以增加光吸收层和衬底之间的联结力。
附图说明
图1至11是示出根据本发明实施例的太阳能电池制造方法的剖视图。
具体实施方式
在实施例的描述中，当各个衬底、层、膜或电极等被表述为形成在其它衬底、层、膜或电极“上”或“下”时，“上”或“下”还表示一个组件“直接地”或“间接地(通过其它组件)”形成到另一组件上。此外，将基于附图描述每个组件的“上”或“下”的标准。在附图中，可以夸大地描绘每个组件的尺寸，并且不意味着实际应用该尺寸。
图11是根据本发明实施例的太阳能电池的剖视图。
如图11所示，实施例的太阳能电池包括衬底100、图案层170、后电极200、光吸收层300、缓冲层400和前电极500。
在此情形中，图案层170包括不平整图案150，可以在不平整图案150中周期性地形成具有四角棱锥或正弦波形状的弯曲部。
此外，如图3所示，不平整图案150包括凹槽110和突起120，凹槽的宽度为100-300nm，突起的宽度为100-200nm，凹槽和突起的高度可以为100-300nm。
通过不平整结构形成凹槽110和突起120，从而使得凹槽120具有从衬底100突起的形状。
此外，凹槽110和突起120使得接触面积可以扩大，可以增强衬底100和之后形成的后电极之间的结合。
具体地，当衬底100是挠性的时，尽管衬底100被弯曲，也可以通过图案层170防止在后电极中产生裂缝。
此外，后电极还形成不平整图案150的凹槽110内部，从而可以增加衬底100和后电极之间的结合力。
图案层170可以由包含树脂的材料形成，该树脂为诸如环氧树脂、环氧树脂三聚氰胺、亚克力和聚氨酯树脂的单一型或混合型树脂。
下文中，将根据太阳能电池的制造过程更详细地描述所述太阳能电池。
图1至11是示出根据本发明实施例的太阳能电池制造方法的剖视图。
首先，如图1所示，包括不平整图案150的图案层170形成在衬底100上。
衬底100使用玻璃也可以使用诸如氧化铝的陶瓷衬底、不锈钢和钛衬底或聚合物衬底等作为其材料。
玻璃衬底可以使用钠钙玻璃，聚合物衬底可以使用PET(polyethylenterephthalate，聚对苯二甲酸乙二醇酯)和聚酰亚胺。
此外，衬底100可以是刚性或挠性的。
在衬底100的表面上形成树脂层之后，不平整图案150可以在树脂层中形成不平整图案。
此时，如图2所示，形成图案的方法包括在衬底100上形成树脂层，并且应用使用模具230的模制过程，同时应用UV硬化过程。
当在衬底100上涂覆树脂层时，进行到旋转涂布过程。
树脂层可以由包含单一型或混合型树脂(诸如环氧树脂、环氧树脂黑素、亚克力和聚氨酯树脂)的材料形成。
然而，形成图案的方法不限于此，在衬底100上形成树脂层之后，可以利用激光源形成所述图案。
图3和4详细示出图1的“A”区域，即，不平整图案150，不平整图案150包括凹槽110和突起120，并且周期性地形成具有正方柱形状的不平整图案150的弯曲部。
通过不平整结构形成凹槽110和突起120，从而使得突起120具有从衬底100突起的形状。
此外，凹槽110和突起120使得接触面积可以扩大，从而可以增大衬底100和之后形成的后电极之间的联结力。
具体地，当衬底100是挠性的时，尽管衬底100被弯曲，但是拉伸应力通过图案层170传递到后电极，由此可以防止裂缝的产生。
在此情形中，凹槽110的宽度f为100-300nm，突起120的宽度g为100-200nm，凹槽110的高度b和突起120的高度c可以为100-300nm。
在本实施例中，不平整图案150包括凹槽110和突起120，但不限于此，并且所述不平整图案150可以通过下述结构形成，该结构形成有能够提高不平整图案150与之后形成的后电极之间的联结力的图案。
尽管附图中未示出，但是具有正方柱形状的不平整图案150可以形成为在一个方向较长。
在此情形中，不平整图案150不限于正方柱，如图4所示，可以周期性地形成具有弯曲的正弦波形状的不平整图案160的弯曲部。
图案层170可以由包含树脂的材料形成，该树脂为诸如环氧树脂、环氧树脂三聚氰胺、亚克力和聚氨酯树脂的单一型或混合型树脂。
当衬底100由聚合物衬底(即PET和聚酰亚胺)形成时，由于图案层170和衬底100之间的联结力强，因此也可以增强衬底100和之后形成的后电极之间的联结力。
此外，如图5和6所示，在图案层170上形成后电极201。
后电极201成为导电层。后电极层201使得从太阳能电池的光吸收层300产生的电荷可以移动，从而电流可以流到太阳能电池外部。后电极层201应该具有高电导率和小电阻率(specific resistance)以执行上述功能。
此外，当在伴随形成CIGS化合物的硫(S)或硒(Se)气氛下进行热处理时，后电极层201应该保持具有高温稳定性。
可以通过钼(Mo)、金(Au)、铝(Al)、铬(Cr)、钨(W)和铜(Cu)中的任意一种形成这样的后电极201。具体地，在它们中间，钼(Mo)通常可以满足后电极层201所需的特性。
后电极层201可以包括至少两层。在此情形中，每层可以由相同金属或互不相同的金属形成。
此时，后电极201也插入不平整图案150的凹槽110内部中，以增加后电极201和衬底100之间的联结力。
后电极201的与图案层170接触的侧面可以形成为具有与图案层170的不平整图案相对应的凹面-凸面，并且后电极201的上表面可以形成为与衬底100平行。
具体地，当衬底100是挠性的时，尽管衬底100由于衬底和后电极之间的热膨胀系数差异而被弯曲，但是通过形成在衬底上的不平整图案150可以防止在衬底100和后电极之间产生裂缝。
在此情形中，衬底100的厚度大于不平整图案150和后电极201的厚度，并且后电极201的厚度大于不平整图案150的厚度。
就是说，衬底100、不平整图案150和后电极201的厚度和尺寸关系可以参照图6表示如下：
(a+b)＝W(c+d)    (1)
(c)＝X(d)    (2)
(d)＝Y(e)    (3)
(f)＝Z(g)    (4)
其中，W的值为0.17-0.43，X的值为0.03-0.15，Y的值为0.04-0.12，Z的值为1-2。
在条件表达式中，a是从不平整图案150的上表面(即突起120的上表面)到后电极图案201的上表面的距离，b是凹槽110的高度，c是突起120的高度，d是在图案层170中从凹槽110的下表面到衬底100的厚度。
此外，e是衬底100的厚度，f是凹槽110的宽度，g是突起120的宽度。
条件表达式(1)示出后电极201和图案层170之间的关系。
如条件表达式(1)所示，(a+b)(即后电极201的整体厚度)可以是(c+d)(即图案层170的整体厚度)的0.17-0.43(W)倍。
在此情形中，当W值小于0.17时，缓冲层，即图案层170的d区域变厚，从而降低衬底100和图案170的粘合性。
此外，当W值大于0.43时，整个后电极201和图案170之间的厚度减小，因此，图案170中d的厚度不足，从而降低防止产生裂缝的缓冲功能。
条件表达式(2)表示突起120或凹槽110在图案层170的整体厚度中所占的百分比。
就是说，突起120的高度c可以是d(即在图案层170中从凹槽110的下表面到衬底100的厚度)的0.03-0.15(X)倍。
此时，当X值小于0.03时，突起120的高度，即c值过小，从而减小与后电极201的粘合面积，同时，不平整图案150过小，从而降低防止产生裂缝的缓冲功能。
此外，当X值大于0.15时，突起120的高度，即c值变大，因此难以制造不平整图案150。此外，当沉积后电极201时，未沉积到凹槽110的下表面上，从而降低防止产生裂缝的缓冲功能。
条件表达式(3)示出衬底100与区域d(即在图案层170中从凹槽110的下表面到衬底100的厚度)之间的关系。
就是说，d值(即从凹槽110的下表面到衬底100的图案层170的厚度)可以是衬底100的厚度的0.04-0.12(Y)倍。
此时，当Y值小于0.04时，d值小，从而降低防止衬底100产生裂缝的缓冲功能。
此外，当Y值大于0.12时，衬底100的厚度相对减小，从而在衬底中容易发生弯折现象，由此容易产生裂缝。
条件表达式(4)示出凹槽110的宽度f和突起120的宽度g之间百分比的关系。
就是说，凹槽110的宽度f可以是突起120的宽度g的1-2(Z)倍。
此外，可以规律或不规律地形成不平整图案150的周期h，并且周期h可以由200-500nm的周期形成。
此外，就衬底100、不平整图案150和后电极201的硬度而言，后电极201比衬底100和不平整图案150硬，衬底100的硬度大于或等于不平整图案150的硬度。
随后，如图7所示，通过向后电极201应用图案化过程形成后电极图案200。
可以通过向后电极201应用光刻过程形成后电极图案200。
此外，后电极图案200可以被布置为条状类型或矩阵类型，以与每个电池对应。
然而，后电极图案200不限于以上类型，并且可以形成为各种类型。
此时，可以通过后电极图案200露出形成在衬底100上的不平整图案150的一部分。
接着，如图8所示，在后电极图案200上形成光吸收层300和缓冲层400。
光吸收层300包括p型半导体化合物。更详细地，光吸收层300包括基于I-III-VI族的化合物。例如，光吸收层300可以具有基于铜-铟-镓-硒(Cu(In，Ga)Se2，基于CIGS)或基于铜-镓-硒的晶体结构。
例如，为了形成光吸收层300，通过利用铜靶、铟靶和镓靶在后电极图案200上形成基于CIG的金属前驱膜。
在下文中，金属前驱膜通过硒化过程与硒反应，以形成基于CIG的光吸收层300。
此外，在形成金属前驱膜的过程和硒化过程期间，包含在衬底100中的碱性成分穿过后电极图案200扩散到金属前驱膜和光吸收层300中。
碱性成分提高光吸收层300的晶粒度，以提高可结晶性。
此外，光吸收层300可以通过共蒸发法由铜、铟、镓和硒(Cu、In、Ga和Se)形成。
光吸收层300接收从外部入射的光，并将所接收的光转换为电能。光吸收层300形成由光电效应产生的光电动势。
此时，光吸收层300的与衬底100接触的部分也形成在不平整图案150上。
就是说，光吸收层300的该部分也与不平整图案150的凹槽110和突起120联结，从而可以增加光吸收层300和衬底100的联结力。
缓冲层400可以由至少一层形成，并且可以通过硫化镉(CdS)、ITO、ZnO和i-ZnO中的任意一种形成缓冲层400，或者通过将它们层叠在形成有光吸收层300的衬底100上形成缓冲层400，并且缓冲层400可以通过掺杂铟(In)、镓(Ga)和铝(Al)而获得低电阻值。
此时，缓冲层400是n型半导体层，光吸收层300是p型半导体层。因此，光吸收层300和缓冲层400形成pn结。
缓冲层400被布置在光吸收层300和之后形成的前电极之间。
就是说，由于光吸收层300和前电极在晶格常数和带隙能量方面差异很大，因此，为了形成良好的结，由于带隙差异而将缓冲层布置在这两种材料之间是必要的。
在本实施例中，尽管缓冲层形成在光吸收层300上，但是本发明不限于此，并且缓冲层400可以由多个层形成。
随后，如图9所示，穿过光吸收层300和缓冲层400形成接触图案。
可以通过应用机械方法或利用激光的过程形成接触图案310，并且露出后电极图案200的一部分。
此外，如图10所示，通过在缓冲层400上层叠透明导电材料，形成前电极500和互连部700。
当在缓冲层400上层叠透明材料时，透明导电材料也插入到接触图案310的内部，以形成互连部700。
后电极图案200和前电极500通过互连部700互相电连接。
通过在衬底100上应用溅射过程由掺杂铝的氧化锌形成前电极500。
作为与光吸收层300形成pn结的窗口层，前电极500被用作太阳能电池前面的透明电极，因此，前电极500由具有高透光率和良好电导率的氧化锌(ZnO)形成。
此时，可以通过向氧化锌掺杂铝来形成具有低电阻值的电极。
通过利用ZnO靶的RF溅射法、利用Zn靶的反应溅射法、和金属有机化学沉积法等沉积法，可以形成前电极500，即氧化锌薄膜。
此外，通过在氧化锌薄膜上沉积具有优异光电特性的ITO(氧化铟锡)薄膜，还可以形成双层结构。
随后，如图11所示，穿过光吸收层300、缓冲层400和前电极500形成分隔图案320。
可以通过应用机械方法或利用激光的过程形成分隔图案320，并且露出后电极图案200的一部分。
缓冲层400和前电极500可以被分隔图案320划分，电池C1、C2中的每个可以被分隔图案320彼此分隔。
光吸收层300、缓冲层400和前电极500可以通过分隔图案320被布置为条状类型或矩阵类型。
分隔图案320不限于上述类型，并且可以形成为各种类型。
通过分隔图案320形成包括后电极图案200、光吸收层300、缓冲层400和前电极500的电池C1、C2。
此时，电池C1、C2中的每个通过互连部700彼此连接。第二电池C2的后电极图案200与接触第二电池C2的第一电池C1的前电极500通过互连部700彼此连接。
上述根据实施例的太阳能电池及其制造方法可以在衬底上形成纳米尺寸的不平整图案，由此提高与形成在衬底上的后电极的联结力。
具体地，当衬底是挠性的时，尽管衬底被弯曲，但是不会在衬底和后电极之间产生裂缝。
就是说，后电极还形成在不平整结构图案的凹槽内部，以增加衬底和后电极之间的联结力。
光吸收层(其一部分与衬底相接触)也与不平整结构图案接触，以增加光吸收层和衬底之间的联结力。
此外，尽管示出和描述了本发明的优选实施例，但是本发明不限于上述具体实施例，并且在不脱离本实施例基本特性的范围内，本领域技术人员可以进行各种变型或应用。例如，在实施例中具体表示的各实施要素可变更实施，这些变更与应用有关的不同之处应理解为包含于权利要求书限定的本发明的保护范围内。

Claims (19)

1.一种太阳能电池，包括：
图案层，布置在衬底上且包括不平整图案；
后电极，布置在所述图案层上；
光吸收层，布置在所述后电极上；
缓冲层，布置在所述光吸收层上；以及
前电极，布置在所述缓冲层上。
2.根据权利要求1所述的太阳能电池，其中，凹槽和突起周期性地形成在所述不平整图案中。
3.根据权利要求2所述的太阳能电池，其中，所述凹槽的宽度为100-300nm，所述突起的宽度为100-200nm，所述凹槽和所述突起的高度为100-300nm，并且包括所述凹槽和所述突起的所述不平整图案的周期为200-500nm。
4.根据权利要求2所述的太阳能电池，其中，就所述衬底、所述图案层和所述后电极而言，其中，a是从所述不平整图案的上表面，即所述突起的上表面，到所述后电极的表面的距离，b是所述凹槽的高度，c是所述突起的高度，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，满足条件表达式(a+b)＝W(c+d)，其中W的值为0.17-0.43。
5.根据权利要求2所述的太阳能电池，其中，就所述图案层而言，其中，c是所述突起的高度，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，满足条件表达式(c)＝X(d)，其中X的值为0.03-0.15。
6.根据权利要求2所述的太阳能电池，其中，就所述衬底和所述图案层而言，其中，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，e是所述衬底的厚度，满足条件表达式(d)＝Y(e)，其中Y的值为0.04-0.12。
7.根据权利要求2所述的太阳能电池，其中，就所述图案层而言，其中，f是所述凹槽的宽度，g是所述突起的宽度，满足条件表达式(f)＝Z(g)，其中Z的值为1-2。
8.根据权利要求1所述的太阳能电池，其中，所述图案层可以由包含树脂的材料形成，该树脂为诸如环氧树脂、环氧树脂三聚氰胺、亚克力和聚氨酯树脂的单一型或混合型树脂。
9.根据权利要求1所述的太阳能电池，其中，所述后电极的与所述图案层接触的侧面被形成为具有与所述图案层的所述不平整图案相对应的凹面-凸面，所述后电极的上表面形成为与所述衬底平行。
10.根据权利要求1所述的太阳能电池，其中，所述不平整图案的宽度从所述衬底朝向所述后电极变窄。
11.一种太阳能电池制造方法，包括：
在衬底上形成包括不平整图案的图案层；
在所述图案层上形成后电极；
在所述后电极上形成光吸收层；
在所述光吸收层上形成缓冲层；以及
在所述缓冲层上形成前电极。
12.根据权利要求11所述的太阳能电池制造方法，其中，形成所述图案层包括：
在所述衬底上形成树脂层；以及
通过对所述树脂层应用利用模具的模制过程同时应用UV硬化过程，来形成具有不平整图案的所述图案层。
13.根据权利要求12所述的太阳能电池制造方法，其中，所述树脂层可以由包含树脂的材料形成，该树脂为诸如环氧树脂、环氧树脂三聚氰胺、亚克力和聚氨酯树脂的单一型或混合型树脂。
14.根据权利要求11所述的太阳能电池制造方法，其中，凹槽和突起周期性地形成在所述不平整图案中。
15.根据权利要求14所述的太阳能电池制造方法，其中，所述凹槽的宽度为100-300nm，所述突起的宽度为100-200nm，所述凹槽和所述突起的高度为100-300nm，并且包括所述凹槽和所述突起的所述不平整图案的周期为200-500nm。
16.根据权利要求14所述的太阳能电池制造方法，其中，就所述衬底、所述图案层和所述后电极而言，其中，a是从所述不平整图案的上表面，即所述突起的上表面，到所述后电极的表面的距离，b是所述凹槽的高度，c是所述突起的高度，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，满足条件表达式(a+b)＝W(c+d)，其中W的值为0.17-0.43。
17.根据权利要求14所述的太阳能电池制造方法，就所述图案层而言，其中，c是所述突起的高度，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，满足条件表达式(c)＝X(d)，其中X的值为0.03-0.15。
18.根据权利要求14所述的太阳能电池制造方法，就所述衬底和所述图案层而言，其中，d是在所述图案层中从所述凹槽的下表面到所述衬底的厚度，e是所述衬底的厚度，满足条件表达式(d)＝Y(e)，其中Y的值为0.04-0.12。
19.根据权利要求14所述的太阳能电池制造方法，就所述图案层而言，其中，f是所述凹槽的宽度，g是所述突起的宽度，满足条件表达式(f)＝Z(g)，其中Z的值为1-2。
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