CN105914241B - 光伏装置和形成光伏装置的方法 - Google Patents
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Abstract
本发明提供了光伏装置和形成光伏装置的方法。所述光伏装置包括:玻璃基底;透明导电氧化物层;Zn1‑xMgxO半导体窗口层,其中,0<x<1;缓冲层,在玻璃基底和Zn1‑xMgxO半导体窗口层之间;以及半导体吸收层,在Zn1‑xMgxO半导体窗口层上,其中,半导体吸收层包括碲化镉,其中,Zn1‑xMgxO半导体窗口层相对于半导体吸收层的导带偏移在0至+0.4eV的范围中。
Description
本申请是申请日为2011年9月21日、申请号为201180056108.7、题为“具有氧化锌镁窗口层的薄膜光伏装置”的专利申请的分案申请。
技术领域
本发明的实施例涉及半导体装置及制造方法,更具体地涉及光伏(PV)装置领域。
背景技术
光伏装置通常包括沉积在基底(例如玻璃)上的多层材料。图1描绘了典型的光伏装置。光伏装置100可以采用玻璃基底105、沉积在基底105上的透明导电氧化物(TCO)层110、由n型半导体材料制成的窗口层115、由半导体材料制成的吸收层120以及金属背接触件125。典型的装置使用碲化镉(CdTe)作为吸收层120并包括玻璃基底105、作为TCO层110的氧化锡(SnO2)或氧化镉锡(Cd2SnO4)和作为窗口层115的硫化镉(CdS)。以示例的方式,基底105上的典型的光伏装置的沉积工艺的顺序为:TCO层110,包括与SnO2和Cd2SnO4中的一种掺杂的n型材料;CdS窗口层115;CdTe吸收层120;以及金属背接触件125。CdTe吸收层120可以沉积在窗口层115的顶部上。
图2中描绘了典型的薄膜光伏装置(例如CdTe装置)的示例性能带图。作为TCO层的F掺杂的SnO2的带隙能被描绘为205,作为缓冲层的未掺杂的SnO2的带隙能被描绘为210,作为窗口层的CdS的带隙能被描绘为215,作为吸收层的CdTe的带隙能被描绘为220。典型地,CdS相对于CdTe的导带边沿偏移Δ通常是-0.2eV,具有+/-0.1eV的实验不确定度。
如图2中所描绘的,Δ是窗口层和吸收层之间的导带边沿Ec的偏差,在CdS/CdTe堆叠的情况下,Δ是大约-0.2eV。理论模型已经表明较大的Δ负值由于光载流子在窗口层/吸收层的界面复合的速率增加而导致Voc和FF的更大的损失。当使Δ略微呈正值(0至0.4eV)时,可以将复合速率最小化,导致改善的Voc和FF。
CdS是包括采用CdTe和Cu(In,Ga)Se2中的一种作为吸收层的光伏装置的许多类型的薄膜光伏装置中的常规的窗口层。然而,如图2中所描绘的,CdS的光带隙仅为2.4eV。
发明内容
根据本发明的一方面,提供了一种光伏装置,所述光伏装置包括:玻璃基底;透明导电氧化物层;Zn1-xMgxO半导体窗口层,其中,0<x<1;缓冲层,在玻璃基底和Zn1-xMgxO半导体窗口层之间;以及半导体吸收层,在Zn1-xMgxO半导体窗口层上,其中,半导体吸收层包括碲化镉,其中,Zn1-xMgxO半导体窗口层相对于半导体吸收层的导带偏移在0至+0.4eV的范围中。
Zn1-xMgxO半导体窗口层可以位于缓冲层上。
Zn1-xMgxO半导体窗口层的厚度范围可以为大约2nm至大约2000nm。
Zn1-xMgxO半导体窗口层的导电率可以在大约1毫欧姆每厘米至大约10欧姆每厘米的范围内。
Zn1-xMgxO半导体窗口层可以用Al、Mn、Nb、N、F掺杂或者引入氧空位。
所述光伏装置还可以包括位于玻璃基底和透明导电氧化物层之间的阻挡层。
半导体窗口层可以具有在大约1×1014cm3和大约1×1019cm3之间的掺杂剂浓度。
半导体窗口层可以具有在大约1×1017cm3和大约1×1018cm3之间的掺杂剂浓度。
根据本发明的另一方面,提供了一种形成光伏装置的方法,所述方法包括:在基底上方形成透明导电氧化物层;在透明导电氧化物层上方形成包括Zn1-xMgxO的第一半导体窗口层,其中,0<x<1;在玻璃基底和Zn1-xMgxO半导体窗口层之间形成缓冲层;以及在Zn1-xMgxO半导体窗口层上方形成半导体吸收层,其中,半导体吸收层包括碲化镉,其中,第一半导体窗口层相对于半导体吸收层的导带偏移在0至+0.4eV的范围中。
所述方法还可以包括:在第一半导体窗口层和半导体吸收层之间形成第二半导体窗口层,其中,第二半导体窗口层包括硫化镉。
半导体吸收层可以位于第一半导体窗口层上。
所述方法还可以包括:用Al、Mn、Nb、N、F或者通过引入氧空位来掺杂第一半导体窗口层。
第一半导体窗口层可以具有在大约1×1014cm3和大约1×1019cm3之间的掺杂剂浓度。
第一半导体窗口层可以具有在大约1×1017cm3和大约1×1018cm3之间的掺杂剂浓度。
第一半导体窗口层可以通过溅射、蒸发沉积、CVD、化学浴沉积工艺和气相传输沉积工艺中的至少一种来形成。
第一半导体窗口层可以被形成为使得其导电率在大约1毫欧姆每厘米至大约10欧姆每厘米的范围内。
附图说明
图1描绘了典型的光伏装置。
图2描绘了典型的薄膜光伏装置的示例性能带图。
图3A描绘了根据一个实施例的基底结构。
图3B描绘了根据另一个实施例的基底结构。
图4描绘了根据另一个实施例的基底结构。
图5A描绘了根据一个实施例的薄膜光伏装置。
图5B描绘了根据另一个实施例的薄膜光伏装置。
图6描绘了根据另一个实施例的薄膜光伏装置。
图7描绘了根据一个实施例的薄膜光伏装置的能带图。
图8A描绘了根据一个实施例的断路电压的图示。
图8B描绘了根据另一个实施例的量子效率的图示。
具体实施方式
本公开涉及一种光伏装置及生产方法。在一个实施例中,采用Zn1-xMgxO用于基底结构的窗口层。图3A描绘了根据一个实施例的基底结构300。基底结构300包括基底305、透明导电氧化物(TCO)层310、缓冲层315和窗口层320。可以典型地采用TCO层310以允许太阳辐射进入光伏装置,TCO层310还可以用作电极。TCO层310可以包括与SnO2和Cd2SnO4中的一种掺杂的n型材料。可以采用窗口层320以减少装置中的光载流子(例如,电子和空穴)的内部损失,窗口层320可以显著地影响包括断路电压(Voc)、短路电流(Isc)和填充因数(FF)的装置参数。在一个实施例中,窗口层320可以允许入射光传递到吸光材料以吸收光。根据一个实施例,为了改善窗口层320的整体发光效率,窗口层320包括Zn1-xMgxO化合物。
在一个实施例中,基底结构300可以包括玻璃基底305以及TCO层310。缓冲层315可以是可选择的。窗口层320(例如Zn1-xMgxO层)可以直接在TCO层310的顶部上,TCO层包括F掺杂的SnO2、未掺杂的SnO2和Cd2SnO4中的一种或多种。当TCO层包括未掺杂的Cd2SnO4时,TCO层不具有外来的掺杂剂,然而该层可能由于氧空位而是高度n型的。
根据另一个实施例,可以提供用于制造光伏装置的基底结构300。如图3A中所描绘的,基底结构包括基底305、TCO层310、低导电率缓冲层315以及Zn1-xMgxO窗口层320。图3A的基底结构包括装置的其他层(例如,吸收层、金属背件等)可以沉积到其上的Zn1-xMgxO窗口层320。在一个实施例中,Zn1-xMgxO窗口层320可以沉积到基于F-SnO2的基底结构(类似TEC10)上。相似地,基底结构300可以是锡酸镉(CdSt)基底结构。缓冲层315可以用于减小在半导体窗口层的形成过程中发生不规则性的可能性。缓冲层315可以由导电率比TCO层310的导电率低的材料形成,例如由未掺杂的氧化锡、氧化锌锡、氧化镉锌或其他透明导电氧化物或者其组合形成。在特定的实施例中,如图4中所描绘的,基底结构300可以不包括缓冲层。当基底结构300包括低导电率缓冲层315时,该缓冲层布置在基底305(例如,玻璃)和Zn1-xMgxO窗口层之间。
在一个实施例中,Zn1-xMgxO窗口层320的厚度范围为从2nm至2000nm。在另一个实施例中,Zn1-xMgxO中的组成x大于0且小于1。窗口层320可以是相对于常规的窗口层材料(例如CdS)导电率更高的材料。另外,窗口层320可以包括允许大大减小在蓝光不足的环境中填充因数(FF)的损失的窗口层材料。Zn1-xMgxO窗口层可以允许在蓝光区域(例如,400nm至475nm)中的更多的太阳辐射能够到达吸收层,导致更高的短路电流(Isc)。
在可选择的实施例中,如图3B中所描绘的,例如基底结构350的光伏装置可以包括作为窗口层320的Zn1-xMgxO化合物材料以及阻挡层和CdS窗口层中的一个或多个。基底结构350的阻挡层355可以是氧化硅、氧化硅铝、氧化锡或其他合适的材料或者其组合。CdS窗口层360可以沉积在Zn1-xMgxO层320上,其中CdS窗口涉及用于沉积吸收层的表面。在一个实施例中,光伏装置除了基底结构(例如,基底结构300)之外还包括Zn1-xMgxO窗口层。例如,基底结构300可以采用包括基底305、TCO层310以及一个或多个附加元件的TCO堆叠件。在另一个实施例中,基底结构300可以包括缓冲层315。
Zn1-xMgxO对于传统的CdS窗口层的优势可以在于Zn1-xMgxO相对于具有CdS窗口层的装置具有更宽的带隙。这样,更多的太阳辐射可以到达CdTe吸收层,这导致更高的Isc。相似地,通过调整Zn1-xMgxO的组成,可以实现改善的导带边沿对准,这产生更高的Voc。掺杂浓度可以在每cm3的金属氧化物为1015至1015原子(或离子)掺杂剂的范围中。Zn1-xMgxO的载流子密度可以大于CdS的载流子密度。这样,可以形成更强的n-p半导体异质结,从而增加了太阳能电池的内置电势并将在界面处的复合最小化。导电率更高的窗口层还可以改善与处于全光照下相比蓝光的百分比大大减小的弱光环境(例如光导电效应)下的填充因数的损失。
参照图4,根据另一个实施例描绘图3A的基底结构。基底结构400包括基底405、TCO层410和Zn1-xMgxO窗口层420。与图3A的基底结构相比,可以以更低的成本制造基底结构400。
根据另一个实施例,可以采用Zn1-xMgxO用于光伏装置的窗口层。图5A至5B描绘了根据一个或多个实施例的光伏装置,所述光伏装置可以形成为薄膜光伏装置。参照图5A,光伏装置500包括基底505、透明导电氧化物(TCO)层510、缓冲层515、窗口层520、吸收层525和金属背接触件530。可以采用吸收层525以在吸收太阳辐射时产生光载流子。金属背接触件530可以被用作电极。金属背接触件530可以由钼、铝、铜或者任何其他高导电材料制成。光伏装置500的窗口层520可以包括Zn1-xMgxO化合物。
更具体地,光伏装置500可以包括一个或多个玻璃基底505、由SnO2或Cd2SnO4制成的TCO层510、缓冲层515、Zn1-xMgxO窗口层520、CdTe吸收层525以及金属背接触件530。缓冲层515可以涉及低导电率的缓冲层,例如未掺杂的SnO2。缓冲层515可以用于减小在半导体窗口层形成的过程中发生不规则性的可能性。吸收层525可以是CdTe层。层的厚度和材料不受图5A-5B中描绘的厚度的限制。在一个实施例中,图5A的装置可以采用图3A的基底。在特定的实施例中,光伏装置500可以包括或者不包括低导电率缓冲层515、吸收层520和金属背接触件530。
光伏装置500可以包括碲化镉(CdTe)、铜铟镓(二)硒化物(CIGS)和非晶硅(Si)中的一个或多个作为吸收层525。在一个实施例中,可以提供在基底结构和吸收层525之间包括Zn1-xMgxO窗口层520的光伏装置,所述基底结构可以包括或不包括低导电率缓冲层515。在特定的实施例中,所述装置除了Zn1-xMgxO窗口层520之外还可以包括CdS窗口层。
在可选择的实施例中,如图5B中所描绘的,光伏装置500可以包括作为窗口层520的Zn1-xMgxO化合物材料以及阻挡层和CdS窗口层中的一个或多个。阻挡层555可以是氧化硅、氧化硅铝、氧化锡或其他合适的材料或者其组合。CdS窗口层560可以沉积在MS1-xOx层520上,其中CdS窗口560提供用于沉积吸收层的表面。
在特定的实施例中,光伏装置500可以不包括缓冲层。图6描绘了包括玻璃基底605、由SnO2或Cd2SnO4制成的TCO层610、MS1-xOx窗口层615、CdTe吸收层620以及金属背接触件625。
图7描绘了根据一个实施例的光伏装置(例如采用CdTe吸收层的光伏装置)的带结构。在图7中,作为TCO层的F掺杂的SnO2的带隙能被描绘为705,作为缓冲层的未掺杂的SnO2被描绘为710,作为窗口层的Zn1-xMgxO被描绘为715,作为吸收层的CdTe被描绘为720。如进一步描绘的,Zn1-xMgxO相对于CdTe的导带边沿偏移Δ可以被调整到0-0.4eV。图3的光伏装置的另一个优势在于相对于CdS可以具有更宽的带隙。
氧化锌(ZnO)和氧化镁(MgO)都是宽带隙氧化物。ZnO具有3.2eV的带隙,MgO具有大约7.7eV的带隙。由于ZnO是高度掺杂的,所以ZnO可更具有优势。如通过模拟所预测的,三元化合物Zn1-xMgxO应当具有至少3eV的带隙,这远大于CdS的带隙,因此该化合物对于蓝光更透明。另一方面,ZnO相对于CdTe的导带边沿具有从-0.6至-0.1eV的Δ,而MgO具有大约2.7eV的正Δ。因此,如图4中所示,可以调整三元化合物Zn1-xMgxO的组成来得到微小的正值Δ。
图8A-8B描绘了可以通过在光伏装置的窗口层中采用Zn1-xMgxO来提供的优势。首先参照图8A,示出了CdS装置805和Zn1-xMgxO装置810的断路电压的图示。
通过用Zn1-xMgxO窗口层代替CdS窗口层而对装置Voc的改进可以包括从810mV至826mV的改进的断路电压。图8B描绘了处于400至600nm的范围内的量子效率855的图示。如图8B中所描绘的,具有Zn1-xMgxO窗口层的描绘为865的CdTe装置从400-500nm相对于描绘为860的CdS窗口层具有更高的量子效率。相对于CdS的21.8mA/cm2的电流密度,Zn1-xMgxO的电流密度可涉及22.6mA/cm2。这里描述的Voc值的改进是示例性的,因为测量特定的改进的增量Δ可能是困难的。源电流可能改进至2mA/cm2,其中相对于CdS装置的改进可以取决于采用的CdS的厚度。
在另一方面,提供了制造图2和图3中所描绘的包括Zn1-xMgxO窗口层的光伏装置和基底的工艺。可以通过一种或多种工艺来制造包括Zn1-xMgxO窗口层的基底结构200,其中可以通过溅射、蒸发沉积和化学气相沉积(CVD)中的一种或多种来制造结构的一个或多个层。相似地,可以通过以下工艺中的一种或多种来制造光伏装置300的Zn1-xMgxO窗口层:包括溅射、蒸发沉积、CVD、化学浴沉积以及气相传输沉积。
在一个实施例中,用于制造光伏装置的工艺通常可以包括DC脉冲溅射、RF溅射、AC溅射和其他溅射工艺中的一种对Zn1-xMgxO窗口层进行的溅射工艺。溅射使用的源材料可以是Zn1-xMgxO三元化合物一种或多种陶瓷靶材,其中x在0至1的范围内。在一个实施例中,用于溅射的源材料可以是Zn1-xMgxO(其中x在0至1的范围内)合金的一种或多种靶材。在另一个实施例中,用于溅射的源材料可以是两种或更多种陶瓷靶材,其中一种或多种由ZnO制成,一种或多种由MgO制成。在另一个实施例中,用于溅射的源材料可以是两种或更多种金属靶材,其中一种或多种由Zn制成,一种或多种由Mg形成。用于溅射Zn1-xMgxO的工艺气体可以是使用不同的混合比例的氩和氧的混合物。
在一个实施例中,可以通过使用包括但不限于二乙基锌、双(环戊二烯)镁的前驱体的利用诸如H2O或臭氧的试剂的大气压化学气相沉积(APCVD)来沉积Zn1-xMgxO窗口层。
根据另一个实施例,制造光伏装置的工艺会导致相对于吸收层的导带偏移。例如,可以通过选择合适的x值将窗口(Zn1-xMgxO)层相对于吸收层的导带偏移调整在0和+0.4eV之间。另外,可以通过用铝(Al)、锰(Mn)、铌(Nb)、氮(N)、氟(F)中的一种掺杂氧化锌镁以及通过导入氧空位来将Zn1-xMgxO窗口层的导电率调节在1毫欧姆每厘米至10欧姆每厘米的范围内。在一个实施例中,掺杂剂浓度是从大约1×1014cm3至大约1×1019cm3。在一个实施例中,使用具有从大约1×1017cm3至大约1×1018cm3的掺杂剂浓度的溅射靶材形成窗口层。
Claims (15)
1.一种光伏装置,所述光伏装置包括:
玻璃基底;
透明导电氧化物层,位于玻璃基底上;
Zn1-xMgxO半导体窗口层,位于透明导电氧化物层上,其中,0<x<1;
缓冲层,在透明导电氧化物层和Zn1-xMgxO半导体窗口层之间;以及
半导体吸收层,在Zn1-xMgxO半导体窗口层上,其中,半导体吸收层包括碲化镉,其中,Zn1-xMgxO半导体窗口层相对于半导体吸收层的导带偏移在0至+0.4eV的范围中。
2.根据权利要求1所述的光伏装置,其中,Zn1-xMgxO半导体窗口层的厚度范围为大约2nm至大约2000nm。
3.根据权利要求1所述的光伏装置,其中,Zn1-xMgxO半导体窗口层的导电率在大约1毫欧姆每厘米至大约10欧姆每厘米的范围内。
4.根据权利要求1所述的光伏装置,其中,Zn1-xMgxO半导体窗口层用Al、Mn、Nb、N、F掺杂或者引入氧空位。
5.根据权利要求1所述的光伏装置,所述光伏装置还包括位于玻璃基底和透明导电氧化物层之间的阻挡层。
6.根据权利要求4所述的光伏装置,其中,半导体窗口层具有在大约1×1014cm-3和大约1×1019cm-3之间的掺杂剂浓度。
7.根据权利要求6所述的光伏装置,其中,半导体窗口层具有在大约1×1017cm-3和大约1×1018cm-3之间的掺杂剂浓度。
8.一种形成光伏装置的方法,所述方法包括:
在基底上方形成透明导电氧化物层;
在透明导电氧化物层上方形成包括Zn1-xMgxO的第一半导体窗口层,其中,0<x<1;
在透明导电氧化物层和Zn1-xMgxO半导体窗口层之间形成缓冲层;以及
在Zn1-xMgxO半导体窗口层上方形成半导体吸收层,其中,半导体吸收层包括碲化镉,其中,第一半导体窗口层相对于半导体吸收层的导带偏移在0至+0.4eV的范围中。
9.根据权利要求8所述的方法,所述方法还包括:在第一半导体窗口层和半导体吸收层之间形成第二半导体窗口层,其中,第二半导体窗口层包括硫化镉。
10.根据权利要求8所述的方法,其中,半导体吸收层位于第一半导体窗口层上。
11.根据权利要求10所述的方法,所述方法还包括:用Al、Mn、Nb、N、F或者通过引入氧空位来掺杂第一半导体窗口层。
12.根据权利要求10所述的方法,其中,第一半导体窗口层具有在大约1×1014cm-3和大约1×1019cm-3之间的掺杂剂浓度。
13.根据权利要求10所述的方法,其中,第一半导体窗口层具有在大约1×1017cm-3和大约1×1018cm-3之间的掺杂剂浓度。
14.根据权利要求10所述的方法,其中,第一半导体窗口层通过溅射、蒸发沉积、CVD、化学浴沉积工艺和气相传输沉积工艺中的至少一种来形成。
15.根据权利要求10所述的方法,其中,第一半导体窗口层被形成为使得其导电率在大约1毫欧姆每厘米至大约10欧姆每厘米的范围内。
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