CN101048877A - 包含光电活性半导体材料的光电池 - Google Patents

包含光电活性半导体材料的光电池 Download PDF

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CN101048877A
CN101048877A CNA2005800368915A CN200580036891A CN101048877A CN 101048877 A CN101048877 A CN 101048877A CN A2005800368915 A CNA2005800368915 A CN A2005800368915A CN 200580036891 A CN200580036891 A CN 200580036891A CN 101048877 A CN101048877 A CN 101048877A
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H-J·施特策尔
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Abstract

本发明涉及一种包含光电活性半导体材料的光电池。所述光电池的特征在于光电活性半导体材料为具有式(I)的二元化合物或具有式(II)的三元化合物的p－掺杂或n－掺杂的半导体材料：ZnTe(I)，Zn1－xMnxTe(II)，其中x为0.01－0.99的数。在所述光电活性半导体材料中的一定比例碲离子由卤离子和氮离子替代且卤离子选自氟离子、氯离子和溴离子或其混合物。

Description

包含光电活性半导体材料的光电池
本发明涉及光电池和存在于其中的光电活性半导体材料。
光电活性材料为将光转换为电能的半导体。其原理已知很长时间且在工业上使用。工业上使用的绝大部分太阳能电池基于晶体硅(单晶或多晶)。在p-和n-导电硅间的界面层中，入射光子激发半导体的电子从而使电子从价带升高到导带。
价带和导带间的禁带宽度的大小限制了太阳能电池的最大可能效率。在硅的情况下，在用阳光辐照时的效率约为30％。相比之下，实际达到约15％的效率，因为部分电荷载体通过不同方法复合并因此不再有效。
DE 102 23 744 A1公开了替代的光电活性材料和其中存在这些材料的光电池，其具有使效率降低程度较小的损耗机理。
由于禁带宽度为约1.1eV，硅具有相当好的实用价值。禁带宽度的降低将促使更多的电荷载体进入导带，但电池电压变低。类似的是较大禁带宽度会得到较高的电池电压，但因为仅有较少光子可用于激发，产生较低可用电流。
已提出许多排列如串联电池中具有不同禁带宽度的半导体的串联，以获得较高的效率。然而，因为其结构复杂这些排列很难在经济上实现。
新的概念包括在禁带宽度中产生中间能级(向上转换)。该概念例如描述于如下文献中：Proceedings of the 14th Workshop on Quantum SolarEnergy Conversion-Quantasol 2002，2002年3月17-23日，Rauris，Salzburg，奥地利，“Improving solar cells efficiencies by theup-conversion”，T1 Trupke，M.A.Green，P.Würfel或“Increasing theEfficiency of Ideal Solar Cells by Photon Induced Transitions atintermediate Levels”，A.Luque和A.Marti，Phys.Rev.Letters，第78卷，第26卷，1997年7月，5014-5017。在1.995eV带隙和0.713eV中间能级能量的情况下，经计算最大效率为63.17％。
该中间能级已例如在体系Cd1-yMnyOxTe1-x或Zn1-xMnxOyTe1-y中通过光谱方法证实。这描述于如下文献中：“Band anticrossing in groupII-OxVI1-X highly mismatched alloys：Cd1-yMnyOxTe1-x quaternariessynthesized by O ion implantation”，W.Walukiewicz等人，Appl.Phys.Letters，第80卷，第9期，2002年3月，571-1573和″Synthesis and opticalproperties of II-O-VI highly mismatched alloys″，W.Walukiewicz等人，J.Appl.Phys.，第95卷，第11期，2004年6月，6232-6238。根据这些作者，通过显著更具电负性的氧离子替代阴离子晶格中的部分碲阴离子而产生带隙中所需的中间能级。这里碲借助薄膜中的离子注入由氧替代。这类材料的显著缺点为氧在半导体中的溶解度非常低。这例如得到热力学上不稳定的化合物Zn1-xMnxTe1-yOy，其中y大于0.001。在延长辐照时间时，化合物分解为稳定的碲化物和氧化物。所希望的是由氧替代至多10原子％碲，但是这类化合物不稳定。
因为带隙大，室温下直接带隙为2.32eV的碲化锌将为中间能级技术的理想半导体。碲化锌中的锌可易于由锰连续替代，其中对于MnTe而言带隙增加至约2.8eV(“Optical Properties of epitaxial ZnMnTe and ZnMgTefilms for a wide rnge of alloy compositions”，X.Liu等人，J.Appl.Phys.第91卷，第5卷，2002年3月，2859-2865；“Bandgap of Zn1-xMnxTe：non linear dependence on composition and temperature”，H.C.Mertins等人，Semicond.Sei.Technol.8(1993)1634-1638)。
Zn1-xMnxTe可掺杂至多0.2摩尔％磷以使其具有p-导电性，其中电导率为10-30Ω-1cm-1(“Electrical and Magnetic Properties of PhosphorusDoped Bulk Zn1-xMnxTe”，Le Van Khoi等人，Moldavian Journal ofPhysical Sciences，第1期，2002，11-14)。锌由铝部分替代得到n-导电性种(“Aluminium-doped n-type ZnTe layers grown by molecular-beamepitaxy”，J.H.Chang等人，Appl.Phys.Letters，第79卷，第6期，2001年8月，785-787；“Aluminium doping of ZnTe grown by MOPVE”，S.I.Gheyas等人，Appl.Surface Science 100/101(1996)634-638；“ElectricalTransport and Photoelectronic Properties of ZnTe：Al Crystals”，T.L.Lavsen等人，J.Appl.Phys.，第43卷，第1期，1972年1月，172-182)。掺杂度为约4*1018Al/cm3时，可获得约50-60Ω-1cm-1的电导率。
本发明目的为提供一种具有高效率和高电功率且避免了现有技术缺点的光电池。本发明的另一目的尤其为提供一种包含在禁带宽度中具有中间能级的热力学上稳定的光电活性半导体材料的光电池。
根据本发明，该目的通过包含光电活性半导体材料的光电池实现，其中光电活性半导体材料为包含式(I)的二元化合物或式(II)的三元化合物的p-或n-掺杂的半导体材料：
                   ZnTe  (I)
             Zn1-xMnxTe  (II)
其中x为0.01-0.99，光电活性半导体材料中的一定比例碲离子已由卤离子和氮离子替代且卤离子选自氟离子、氯离子和溴离子及其混合物。
在ZnTe或Zn1-xMnxTe中，碲离子不易由卤离子替代。卤离子带有单个负电荷。因此带两个负电荷的碲离子将必须由两个卤离子替代，这在高掺杂浓度下是不可能的。为此由本发明提供的方案包括由卤离子和带有三个负电荷的氮离子替代碲离子。Te2-可由半径为1.71的N3-替代，区别在于相对于Te2-其电负性为0.94。卤素和氮的摩尔比可为1∶1。令人惊讶的是卤素和氮的其它摩尔比也是可以的。
含有锰的合金易于插入氮如N3-，因而本发明提供的方案尤其涉及x＝0.01-0.09的式Zn1-xMnxTe的三元半导体。
本发明光电池优点为所用光电活性半导体材料甚至在碲由卤素和氮(令人惊讶的是不仅卤素和氮的摩尔比为1∶1时)替代之后也热力学稳定。此外，本发明的光电池具有高效率(至多＞20％)，因为碲离子由卤离子和氮离子替代在光电活性半导体材料的禁带宽度中产生中间能级。如果没有中间能级，则只有具有至少禁带宽度能量的光子能使电子或电荷载体从价带升高至导带。具有较高能量的光子也有助于效率，其中与带隙相比过量的能量作为热量损失。在根据本发明使用的半导体材料中存在且可被部分占领的中间能级的情况下，更多光子可有助于激发。
本发明光电池包含p-掺杂的半导体材料和n-掺杂的半导体材料，其中这两种半导体材料邻接以形成p-n转变。p-掺杂的半导体材料和n-掺杂的半导体材料均基本包含式(I)的二元化合物或式(II)的三元化合物，其中部分碲离子已由卤离子和氮离子替代且在p-掺杂的半导体材料中材料额外掺杂了给电子离子，以及在n-掺杂的半导体材料中材料额外掺杂了受电子离子。这里p-掺杂的半导体材料可含有不同于n-掺杂的半导体材料中那些卤离子的卤离子或卤离子混合物。
根据本发明，光电活性半导体材料含有氟离子、氯离子或溴离子或其混合物作为卤离子。因此包含式(I)的二元化合物或式(II)的三元化合物的半导体材料中的碲离子部分由氟离子、氯离子或溴离子和氮离子替代。这三种卤离子具有有利于替代的离子半径。碲离子的离子半径为2.11，氟离子的半径为1.33，氯离子的半径为1.81，溴离子的半径为1.96。在氟离子的情况下鲍林电负性相对于碲(2.1)电负性的差别为1.88，在氯离子的情况下为1.06以及在溴离子的情况下为0.86。
在本发明的优选实施方案中，氮和卤素分别以0.1-20原子％，优选0.2-10原子％的原子浓度存在于光电活性半导体材料中。在氮和卤素或卤素的混合物的该原子浓度下，有利的是中间能级存在于光电活性半导体材料的禁带宽度中且可使得本发明光电池的效率增加。
p-掺杂半导体材料优选含有原子浓度为至多0.5原子％的As和P中的至少一种元素，n-掺杂半导体材料优选含有原子浓度为至多0.5原子％的Al、In和Ga中的至少一种元素。优选的掺杂元素为铝和磷。
在本发明光电池的优选实施方案中，光电池包括导电基材，厚度为0.1-10μm，优选0.3-3μm的p-掺杂半导体材料的p层，厚度为0.1-10μm，优选0.3-3μm的n-掺杂半导体材料的n层。基材优选为柔性金属箔或柔性金属片。柔性基材与薄光电活性层的组合的优点为不必使用复杂且因此昂贵的用于固定包含本发明光电池的太阳能模件的支架。在非柔性基材如玻璃或硅的情况下，必须借助复杂的支架结构驱散风力以避免太阳能模件的破裂。另一方面，如果柔性可产生变形，则可使用在变形力下不必呈刚性的非常简单且便宜的支架结构。对本发明而言尤其可将不锈钢片用作优选的柔性基材。
在本发明的优选实施方案中，存在于n层中的n-掺杂的半导体材料具有相应于(III)或(IV)的组成：
              ZnTe1-2yHalyNy            (III)
              Zn1-xMnxTe1-2yHalyNy    (IV)
其中x＝0.01-0.99，y＝0.01-0.2和z＝0.0001-0.01，且掺杂了磷、砷或其混合物，存在于p层中的p-掺杂的半导体材料具有相应于式(V)或(VI)的组成：
              ZnTe1-2yHalyNy            (V)
              Zn1-xMnxTe1-2yHalyNy    (VI)
其中x＝0.01-0.99，y＝0.01-0.2和z＝0.0001-0.01，且掺杂了铝、铟、镓或其混合物。
本发明进一步提供了一种生产本发明光电池的方法，其包括用至少两层包含式(I)或(II)化合物的p-或n-掺杂的半导体材料涂覆导电基材，其中各层厚度为0.1-10μm，优选0.3-3μm。因此在本发明导电基材上产生至少一层各自p-或n-掺杂的半导体材料的薄层。
用p或n层涂覆基材优选包括至少一种选自溅射、电化学沉积或化学沉积的沉积方法。可借助各个沉积方法将预先p-或n-掺杂的包含式(I)的二元化合物或式(II)的三元化合物的半导体材料作为层施加至基材。作为其替代，可首先借助沉积方法产生没有p-或n-掺杂的半导体材料层，然后将该层p-或n-掺杂。根据本发明半导体材料中由卤离子和氮离子部分替代碲离子(如果由上述沉积方法产生的各个层仍不具有合适结构)优选在沉积方法之后(以及如果合适的话在p-或n-掺杂之后)进行。
一种可行的沉积方法为通过溅射涂覆。术语溅射是指原子借助加速离子从用作电极的溅射靶中喷出以及喷出材料在基材上的沉积。为涂覆本发明的基材，将Zn1-xMnxTe:Al和Zn1-xMnxTe:P的溅射靶例如用于溅射或将半导体材料的各组分依次溅射至基材上，随后加热至400-900℃的温度。
当通过将组分熔融在一起而产生例如具有组成Zn1-xMnxTe:Al或Zn1-xMnxTe:P的溅射靶时，在溅射方法中产生准备掺杂的半导体层。冒号后的元素为掺杂元素。随后用卤素和氮掺杂以该方式产生的层。
也可通过溅射将组分Zn、Mn、Te和Al或P依次施加至基材上，然后将以该方式产生的层加热至400-900℃的温度，以产生热力学稳定的组成。该组成由各组分通过基材上的固相反应形成。
此外，可使用具有组成ZnTe或Zn1-xMnxTe的溅射靶或可通过溅射将组分Zn、Te和如果合适的话Mn依次施加至基材上以形成层。在这些情况下，p-或n-掺杂和卤素和氮的引入均在本发明光电池的单独生产步骤中进行。
根据本发明可使用的沉积方法的另一优选实施方案为例如使Zn1-xMnxTe在导电基材上电化学沉积。ZnTe的电化学沉积而不是混合的Zn/Mn/Te层的电化学沉积描述于如下文献中：“Thin films of ZnTeelectrodeposited on stainless steel”，A.E.Rakhsan和B.Pradup，Appl.Phys.A(2003)，2003年12月19日网上出版，Springer-Verlag；“Electrodeposition of ZnTe for photovoltaic alls”，B.Bozzini等人，ThinSolid Films，361-362，(2000)288-295；“Electrochemical deposition of ZnTeThins films”，T.Mahalingam等人，Semicond.Sci.Technol.17(2002)469-470；“Electrodeposition of Zn-Te Semiconductor Film from AcidicAqueous Solution”，R.Ichino等人，Second Internat.Conference onProcessing Materials for Properties，The Minerals，Metals & MaterialsSociety，2000和美国专利4,950,615。
本发明方法也可包括通过在30-90℃的温度下和在基材存在下借助次磷酸(H3PO2)作为还原剂使包含Zn2+、Mn2+和TeO3 2-离子的水溶液交联而使Zn1-xMnxTe层化学沉积。次磷酸使TeO3 2-还原为Te2-。也可以该方式在非导电基材上沉积。
取决于沉积方法，可能需要将卤素和氮掺入层中以及有时引入掺杂剂的后处理。
在本发明的优选实施方案中，本发明方法包括如下方法步骤：
a)用ZnTe或Zn1-xMnxTe的第一层涂覆导电基材，
b)用卤离子和氮离子掺杂第一层，
c)通过用给电子原子或受电子原子掺杂建立p-或n-掺杂，
d)用ZnTe或Zn1-xMnxTe的第二层涂覆第一层，
e)用卤离子和氮离子掺杂第二层，
f)通过用受电子原子或给电子原子掺杂建立p-或n-掺杂，和
g)将导电透明层和保护层施加至第二层上。
在步骤a)中，导电基材例如通过溅射、电化学沉积或化学沉积涂覆ZnTe或Zn1-xMnxTe的第一层。基材优选为金属片或金属箔。
然后在步骤b)中用卤素和氮掺杂该第一层。这例如可通过在500-1200℃的温度下在氮气或氩气中用卤化铵处理该层而进行。在该温度下，卤化铵为气态且部分离解为氮化NH3和卤化HCl。
随后在步骤c)中，建立p-或n-掺杂通过用给电子原子或受电子原子掺杂进行。例如将第一层或者用磷(例如PCl3)掺杂形成p导体或者用铝(例如AlCl3)掺杂形成n导体。
在步骤d)中，然后使ZnTe或Zn1-xMnxTe的第二层沉积在第一层上。为此例如可使用与步骤a)中相同的沉积方法。
在步骤e)中，将氮和卤素如对步骤b)中第一层所述而引入第二层中。
在步骤f)中建立的掺杂与步骤c)中建立的掺杂相反，从而使一层为p-掺杂而另一层为n-掺杂。
最后，在步骤g)中将导电透明层和保护层施加至第二层上。导电透明层例如可为铟-锡氧化物或铝-锌氧化物层。此外，优选其具有用于在本发明光电池上建立电接触的导体轨道(conductor track)。保护层优选为SiOx层，其中x＝1-2。
实施例1
将5.16g Zn、1.01g Mn和12.76g Te称重入直径为10mm，长度为200mm的熔凝硅管中，其中所有元素具有大于99.995％的纯度。将熔凝硅管抽空并在减压下火焰密封。然后在管式炉中经过20小时使其达到1250℃，同时使纵轴倾斜(时间：约90秒)，在该温度维持5小时，然后使炉冷却。获得一块组成为Zn0.8Mn0.2Te且在光学反射光谱中的带隙为2.28eV的熔凝材料。
为用卤离子和氮离子掺杂该材料，将1.8g材料和16mg氯化铵称重入另一熔凝硅管中。在减压下将熔凝硅管火焰密封。在水平管式炉中将其在500℃下加热5小时。然后关掉炉子。以该方式所得试样含有0.45原子％N和2.0原子％Cl-。其在1.380nm显示有额外的吸收，该吸收相应于作为中间能级的0.9eV能量。
实施例2
为进行电化学沉积，在配有双层壁、内部温度计和底部出口阀的500ml玻璃法兰容器中进行电解。将不锈钢片(100×70×0.5)用作阴极。阳极包含MKUSF04(石墨)。
a)制备ZnTe
将21.35g ZnSO4.7H2O和55.4mg Na2TeO3溶于蒸馏水中。借助H2SO4(2mol/L)将溶液的pH调至2，随后用蒸馏水将该溶液补足500ml(Zn＝0.15mol/L；Te＝0.5mmol/L；Zn/Te＝300/1)。随后将电解质溶液放入电解电池中并加热至80℃。在100.0mA电流下电解30分钟且不搅拌。在～50cm2(2mA/cm2)的阴极面积中进行沉积。电解完成后，取出阴极，用蒸馏水漂洗并干燥。沉积出铜色的膜(18.6mg)。
b)制备Zn1-xMnxTe
将21.55g ZnSO4·7H2O(0.15mol/L)、47.68g MnSO4·H2O(0.6mol/L)、33g(NH4)2SO4(0.5mol/L)、1g酒石酸和55.4mg Na2TeO3(0.5mmol/L)溶于蒸馏水中。借助H2SO4(2mol/L)将该溶液的pH调至2，随后用蒸馏水将该溶液补足500ml(Zn/Mn/Te＝300/1200/1)。随后将电解质溶液放入电解电池中并加热至80℃。在101.3mA电流下电解60分钟且不搅拌。在～50cm2(～2mA/cm2)的阴极面积中进行沉积。电解完成后，取出阴极，用蒸馏水漂洗并干燥。重量增加26.9mg。沉积为深棕褐色。

Claims (12)

1.一种包含光电活性半导体材料的光电池，其中所述光电活性半导体材料为包含式(I)的二元化合物或式(II)的三元化合物的p-或n-掺杂的半导体材料：
                    ZnTe        (I)
                    Zn1-xMnxTe  (II)
其中x为0.01-0.99，
且所述光电活性半导体材料中的一定比例碲离子已由卤离子和氮离子替代
且所述卤离子选自氟离子、氯离子和溴离子及其混合物。
2.根据权利要求1的光电池，其中氮和卤素各自以0.1-20原子％的原子浓度存在于所述光电活性半导体材料中。
3.根据权利要求1或2的光电池，其中所述p-掺杂半导体材料含有原子浓度为至多0.5原子％的As和P中的至少一种元素，所述n-掺杂半导体材料含有原子浓度为至多0.5原子％的Al、In和Ga中的至少一种元素。
4.根据权利要求1-3中任一项的光电池，其包括导电基材，厚度为0.1-10μm的所述p-掺杂半导体材料的p层和厚度为0.1-10μm的所述n-掺杂半导体材料的n层。
5.根据权利要求4的光电池，其中所述基材为柔性金属箔或柔性金属片。
6.根据权利要求4或5的光电池，其中所述存在于n层中的n-掺杂半导体材料具有相应于(III)或(IV)的组成：
            ZnTe1-2yHalyNy               (III)
            Zn1-xMnxTe1-2yHalyNy         (IV)
其中x＝0.01-0.99，y＝0.01-0.2和z＝0.0001-0.01，
且掺杂了磷、砷或其混合物，所述存在于p层中的p-掺杂半导体材料具有相应于式(V)或(VI)的组成：
            ZnTe1-2yHalyNy                (V)
            Zn1-xMnxTe1-2yHalyNy          (VI)
其中x＝0.01-0.99，y＝0.01-0.2和z＝0.0001-0.01，
且掺杂了铝、铟、镓或其混合物。
7.一种生产根据权利要求1-6中任一项的光电池的方法，其中用至少两层包含式(I)或(II)化合物的p-或n-掺杂的半导体材料涂覆导电基材，其中各层厚度为0.1-10μm。
8.根据权利要求7的方法，其中所述涂覆方法包括至少一种选自溅射、电化学沉积或化学沉积的沉积方法。
9.根据权利要求8的方法，其中对溅射而言，
i)Zn1-xMnxTe:Al和Zn1-xMnxTe:P的溅射靶通过将组分熔融在一起而产生，或
ii)将所述半导体材料的各组分依次溅射至所述基材上，随后加热至400-900℃的温度。
10.根据权利要求8的方法，其中通过在30-90℃的温度下和在所述基材存在下借助次磷酸H3PO2作为还原剂使包含Zn2+、Mn2+和TeO3 2-离子的水溶液交联而进行化学沉积。
11.根据权利要求8-10中任一项的方法，其包括如下方法步骤：
a)用Zn1-xMnxTe或ZnTe的第一层涂覆所述导电基材，
b)用卤离子和氮离子掺杂第一层，
c)通过用给电子原子或受电子原子掺杂建立p-或n-掺杂，
d)用Zn1-xMnxTe或ZnTe的第二层涂覆第一层，
e)用卤离子和氮离子掺杂第二层，
f)通过用受电子原子或给电子原子掺杂建立n-或p-掺杂，和
g)将导电透明层和保护层施加至第二层上。
12.根据权利要求11的方法，其中在步骤b)和e)中，在500-1200℃的温度下在氮气或氩气中用卤化铵处理所述层而掺杂卤离子和氮离子。
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CN104627968B (zh) * 2015-01-30 2016-08-24 宁波工程学院 一种p-型Mn-Zn-Te中高温热电化合物的制备工艺

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ATE554502T1 (de) 2012-05-15
CN101048877B (zh) 2010-05-12
US20090133745A1 (en) 2009-05-28
KR20070084275A (ko) 2007-08-24
CA2585166C (en) 2013-04-23
CA2585166A1 (en) 2006-05-04
EP1807872A1 (de) 2007-07-18
US7847187B2 (en) 2010-12-07
JP2008518449A (ja) 2008-05-29
JP4589400B2 (ja) 2010-12-01
EP1807872B1 (de) 2012-04-18
AU2005298837B2 (en) 2011-02-24
DE102004052012A1 (de) 2006-04-27
WO2006045600A1 (de) 2006-05-04

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