CN101517122B - 用于沉积氧化物层到太阳能电池的吸收体上的方法、太阳能电池和该方法的用途 - Google Patents
用于沉积氧化物层到太阳能电池的吸收体上的方法、太阳能电池和该方法的用途 Download PDFInfo
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- CN101517122B CN101517122B CN2007800357360A CN200780035736A CN101517122B CN 101517122 B CN101517122 B CN 101517122B CN 2007800357360 A CN2007800357360 A CN 2007800357360A CN 200780035736 A CN200780035736 A CN 200780035736A CN 101517122 B CN101517122 B CN 101517122B
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- Photovoltaic Devices (AREA)
Abstract
本发明涉及一种用于采用高电离化物理气相沉积(PVD)技术，通过高能脉冲磁控管溅射(HPPMS)或高能推动磁控管溅射(HIPIMS)沉积至少一个稳定的、透明导电层系统到黄铜矿太阳能电池吸收体上的方法，一种太阳能电池以及该方法的用途。
Description
本发明涉及一种方法，用于通过高电离化物理气相沉积(PhysicalVapour Deposition；以下简称：PVD)技术，采用高能脉冲磁控管溅射(HighPower Pulsed Magnetron Sputtering；以下简称：HPPMS)或高能推动磁控管溅射(High Power Impulse Magnetron Sputtering；以下简称：HIPIMS)沉积至少一个稳定的、透明的以及导电层系统到黄铜矿太阳能电池吸收体上。
当前用于制造黄铜矿太阳能吸收体(简称吸收体)的前接触层和缓冲层的方法存在前层系统稳定性不足的缺陷，其导致潮湿作用下的退化，通过在非封闭组件上进行湿热试验时测得。该湿热稳定性可以通过测量前接触层的层阻力，或在上升的温度和空气湿度下于存储太阳能电池或层之后测量太阳能电池的效率来测得。
稳定性不足的原因尤其是粗糙的吸收体表面。沉积在其上的层没有完全覆盖该表面，其导致不稳定。
基于采用ZnO:X(氧化锌：X)(X代表一元素，例如：铝(Al)、镓(Ga)、铟(In)等用于掺杂该氧化物)作为透明前接触的黄铜矿半导体的封闭太阳能组件，通过高效率和良好稳定性来区别。这些组件通过了在增加的温度和空气湿度下(湿热试验，85％的水分，85℃)的人工老化试验，且能够根据EN/IEC 61646被鉴定。然而，在非封闭组件的情况下，观察到一严重的退化(Klenl，用于薄膜太阳能电池和其他应用的透明导电氧化物(TransparentConductive Oxide；以下简称：TCO)(TCO for Thin-film Solar Cells andOther Applications)I-II，讨论会，弗赖堡/瓮施特鲁特(Freyburg/Unstrut)(2005)p.71和79)。退化的增加本质上可以归因于 ZnO:X层表面阻力的增加[Klaer，Proc.19th欧洲光电太阳能会议(EuropeanPhotovoltaic Solar Energy Conf.)，巴黎(2004)1847]。
硫化镉(CdS)层在用于制造异质接触的黄铜矿太阳能电池中被用作为标准。为了这个目的，CdS具有良好的频带和光栅适应性。引起光电流损失的低频带范围是不利的。出于这个原因，该CdS层被涂覆地相对薄(～40nm)，与厚的(～800nm)ZnO前接触层相结合[Potter，Proc.，18thIEEE光电专家会议(Photovoltaic Specialists Conf.)，Las Vegas(1985)，1659]。这采用化学水浴沉积(chemical bath deposition；以下简称：CBD)来发生，CBD确保在非常薄层情况下最佳的覆盖均匀。
为了改进太阳能电池的稳定性，一固有ZnO层(intrinsic ZnO；以下简称：i-ZnO)被涂覆在CdS和掺杂质的ZnO:X层之间。除改进的湿热稳定性之外，该i-ZnO层对电太阳能电池参数没有影响(Ruckh等人，25thIEEE光电专家会议(Photovoltaic Specialists Conf.)(1996)825；Kessler等人，16th欧洲光电太阳能会议(European Photovoltaic Solar Energy Conf.)(2000)775)。没有i-ZnO，可获得相同效率(Ramanathan等人，31st IEEE光电专家会议(Photovoltaic Specialists Conf.)(2005))。
局部缺陷，例如，在吸收体中的小孔，如果它们发生与该前接触的直接接触，则会导致短路(Rau 01等人，薄实心膜(Thin Solid Films)387，(2001)141)。
在湿热试验之后，非封闭太阳能组件必须被显露地标注出严重退化的日期，该退化主要归因于将TCO层沉积到粗糙吸收体上的过程中所产生的粗晶粒边界(空穴)。因此，沉积到逐如玻璃或硅这样的平坦基板上的TCO层显示出无退化，同时，在同样的测试条件下，织纹粗糙的硅片上的这些层显示出严重的退化。这可以归因于由粗糙吸收体表面所导致的ZnO:X的被破坏的微结构(空穴)(Klenk等人和Menner等人，用于薄膜太阳能电池及其他应用的TCO(TCO for Thin-film Solar Cells and Other Applications)III，讨论会，弗赖堡/瓮施特鲁特(Freyburg/Unstrut)(2005)p.79和p.71)
如Kouznetsov等(表面和涂层技术(Surface and Coating Technologies)122(1999)290)所示，可以通过高电离化制造成没有空穴的具有高纵横比的结构。
以下，本发明的目的是提供一种方法，其实现太阳能电池的制造，该太阳能电池具有在水份和/或热(湿热稳定性)影响下拥有改进稳定性的前接触层或缓冲层。
该目的通过沉积至少一个透明导电氧化层到具有至少一个吸收层的太阳能电池上来实现，该沉积采用脉冲频率为500Hz至100Hz、能量密度为至少0.5kW/cm2的脉冲磁控管溅射法来实现。以下方法可用于制造太阳能电池，该方法为沉积至少一个透明导电氧化层到具有至少一个吸收层的太阳能电池上，采用脉冲频率为500Hz至100Hz、能量密度为至少0.5kW/cm2的脉冲磁控管溅射法来实现该沉积。进一步的，脉冲长度≤200μs。进一步的，该脉冲长度为10至200μs。更进一步的，该脉冲长度为30至150μs。一种使用上述方法制造的太阳能电池。
根据本发明，提供了一种方法，该方法用于沉积至少一个透明的、导电氧化层到具有至少一个用于吸收光的吸收层的太阳能电池上，采用脉冲磁控管溅射法来实现该氧化物的沉积。
该脉冲频率在至少100Hz(赫兹)的范围内，优选在1000至100Hz的范围内，尤为特别优选在100至500Hz的范围内。占空因数小于5％。脉冲长度小于200μs(微秒)，特别优选10至200μs，尤为特别优选30至150μs。
因此该溅射方法有利地为高能脉冲磁控管溅射(HPPMS)和/或高能推动磁控管溅射(HIPIMS)。
该方法的一有利实施例提供的是，该粒子束流的能量密度为至少0.5kW/cm2(千瓦每平方厘米)，优选至少0.75kW/cm2，尤为特别优选至少1kW/cm2。
通过采用这种类型的真空沉积方法，当撞击到要被涂层的基板上时，形成层的粒子可以达到较高程度的离子化和/或增加的动能，作为其结果，可以 确保增强在基板表面上被吸收品种的灵活性。
因此，抑制了缺点的形成，尤其是在要被涂层的吸收体的晶界处粗晶粒边界的生成。结果，在湿热试验中可以实现增强沉积在粗糙基板上的TCO层的稳定性。
改进的湿热稳定性对于太阳能组件的工业制造是至关重要的优势，因为可以降低对组件封闭的要求，即，可以节省封装。特别的，这对于在诸如高分子膜和金属箔片这样的柔性基板上制造太阳能组件是有利的，因为此时用玻璃封装是不可能的，为了保持柔性，再次代替的求助对象必须被制成箔片或薄膜封装。
在一优选实施例中，该氧化层被涂覆作为太阳能电池的前接触层，即该层形成太阳能电池的密封上层。前接触层由此被涂覆为1nm至200nm的厚度，优选在100nm至1.5μm之间，优选在300nm至1000nm之间，特别优选在400nm至800nm之间，根据溅射工艺被实施的时间长度而定。
优选的，通过溅射工艺形成前接触层的材料由此包括下述组所形成的氧化物，该组包括氧化锌、氧化铟、氧化锡、锌-锡混合物(锡酸盐)、氧化钛和/或其混合物。
此外，如果所采用的氧化材料是掺杂质的，对于增加导电性和/或调整特定电特性是有利的。根据本发明，掺杂质没有因此限制为特定的掺杂材料，但是根据所期待的结果可以从本领域技术人员所知的材料中选择，优选为铝、镓、铟、硼(B)、氟(F)、锑(Sb)、铌(Nb)和/或其混合物。按照本领域技术人员所知的以及根据所使用的氧化矩阵选择的方式开始掺杂质。例如，对于氧化锌矩阵，优选铝、镓、铟和/或硼用作为掺杂物。对于一氧化铟矩阵，优选锡(铟锡氧化物(Indium Tin Oxides；以下简称：ITO)或锌(铟锌氧化物(Indium Zinc Oxides；以下简称：IZO)是可能的，同时，轮到氧化锡，优选采用元素氟(F)和/或锑(Sb)进行掺杂。最后氧化钛通常提供铌(Nb)作为掺杂物。
在一有益的改进中，掺杂的程度按原子计算在0.2％至5％之间。
在本发明一可供选择的有益实施例中，氧化层被设定为吸收体和处于其上的其他层之间的缓冲层。根据本发明，应该理解的是，首先，该缓冲层被涂覆在吸收体上，且随后至少一个其他层被沉积在该缓冲层上，以便该缓冲层被围在吸收体和其他层之间。当然，对于应用该层作为前层，这个可供选择的实施例结合了提及的相同的优点。
理论上，采用本发明该方法，可以设置任意厚度的缓冲层，然而，有益的是缓冲层被涂覆的厚度在1nm至200nm之间，优选在10至100nm之间，尤为特别优选在10至50nm之间。
因为被吸收品类的灵活性增加，甚至在薄缓冲层(d＜100nm)的情况下，特别是在层的层厚度小于50nm的情况下，可以实现吸收体的隆起的三维结构的完全覆盖。结果，产生一合适的非均过渡。
特别地，有益效果可以作为结果被实现，如果该缓冲层包含的材料从下述组中选择，该组包括元素铟、钨、钼、锌、镁的硫化物和/或硒化物、氧化铟、锌-镁氧化物和/或其混合物。可以通过例如：混合锌-镁硫化物和/或硒化物来理解。
通过采用本发明的方法，在试验中，进一步的优点已经被显现出来，缓冲层中镉的使用可以省却。省却化学水浴沉积形成的CdS层具有优点，一方面，因为在吸收体的制造和TCO沉积之间，组件不再需要被拿到大气压力下，所以在太阳能组件制造过程中可以实现大量简化。另一方面，可以通过使用其他材料而省却含Cd层的使用。
如果太阳能电池具有黄铜矿制造的吸收体，则本发明的方法可以尤为有利地应用。依据本发明的吸收体也包括PV吸收体，特别是粗糙的吸收体，以及薄膜吸收体，例如：铜铟镓硒(CIGS)、碲化镉(CdTe)、非晶硅、微晶硅或由多晶硅或单晶硅制成的，均包括在其内。
根据本发明，同样地提供一太阳能电池，其特征在于至少该前接触层和/ 或该缓冲层根据上述方法制造而成。
使用本发明方法的目的关系到太阳能电池的制造。
下面参考具体实例对本发明做详细描述，且此处不将本发明限制在复制的特殊实施例中。
实例
为测试该方法，ZnO:Al层采用一HPPMS发生器被涂覆到被传送的迷你组件上，该组件的版式为10×10cm2，层结构为玻璃/钼(Mo)/铜-铟-镓-硫(Cu-In-Ga-S)吸收体/CdS/i-ZnO。该相同的吸收体同样地由测试协会提供一最佳的标准的直流(DC)溅射的ZnO:Al层。这些层均具有相同的ZnO-Al层厚度。随后，所制造的非封闭迷你组件经受一湿热试验(在85℃下85％相对湿度)
在表面阻力或效率的变化结果复制在表1中。
表1
表1说明，在非最佳条件下采用HPPMS技术制造的ZnO:Al层显示出改进的湿热稳定性。该测试可根据DIN EN 61646，特别是第20页来实现。
Claims (23)
1.一种用于沉积至少一个透明导电氧化层到具有至少一个吸收层的太阳能电池上的方法，其特征在于：
采用脉冲频率为500Hz至100Hz、能量密度为至少0.5kW/cm2的脉冲磁控管溅射法来实现该沉积。
2.根据权利要求1所述的方法，其特征在于：脉冲长度≤200μs。
3.根据权利要求2所述的方法，其特征在于：该脉冲长度为10至200μs。
4.根据权利要求3所述的方法，其特征在于：该脉冲长度为30至150μs。
5.根据权利要求1～4任一所述的方法，其特征在于：该溅射法是“高能脉冲磁控管溅射”和/或“高能推动磁控管溅射”。
6.根据权利要求1～4任一所述的方法，其特征在于：所述能量密度为至少0.75kW/cm2。
7.根据权利要求6所述的方法，其特征在于：所述能量密度为至少1kW/cm2。
8.根据权利要求1～4任一所述的方法，其特征在于：该氧化层被涂覆作为该太阳能电池的前接触层。
9.根据权利要求8所述的方法，其特征在于：该前接触层的涂覆厚度在100nm和1.5μm之间。
10.根据权利要求9所述的方法，其特征在于：该前接触层的涂覆厚度在300nm和1000nm之间。
11.根据权利要求10所述的方法，其特征在于：该前接触层的涂覆厚度在400nm和800nm之间。
12.根据权利要求8所述的方法，其特征在于：该前接触层包含从下述组中选择的氧化物，该组包括氧化锌、氧化铟、氧化锡、氧化钛和/或其混合物。
13.根据权利要求12所述的方法，其特征在于：该氧化物掺有杂质。
14.根据权利要求13所述的方法，其特征在于：该掺杂材料从下述组中选择，该组包括铝、镓、铟、硼、氟、锑、铌和/或其混合物。
15.根据权利要求13或14的方法，其特征在于：该掺杂按原子计算在0.2％至5％之间。
16.根据权利要求1～4任一所述的方法，其特征在于：缓冲层被涂覆在吸收层上，随后至少一个透明导电氧化层被作为前接触层沉积在该缓冲层上，以便该缓冲层被围在该吸收层和该至少一个透明导电氧化层之间。
17.根据权利要求16所述的方法，其特征在于：该缓冲层的涂覆厚度在1nm和200nm之间。
18.根据权利要求17所述的方法，其特征在于：该缓冲层的涂覆厚度在10nm和100nm之间。
19.根据权利要求18所述的方法，其特征在于：该缓冲层的涂覆厚度在10nm和50nm之间.
20.根据权利要求16所述的方法，其特征在于：该缓冲层包含从下述组中选择的材料，该组包括元素铟、钨、钼、锌、镁的硫化物和/或硒化物、氧化铟、锌-镁氧化物和/或其组合物。
21.根据权利要求16所述的方法，其特征在于：该缓冲层不含镉。
22.根据权利要求1～4任一所述的方法，其特征在于：该太阳能电池具有一吸收体。
23.根据权利要求22所述的方法，其特征在于：所述吸收体为薄膜吸收体，由铜铟镓硒、碲化镉、非晶硅、微晶硅制成，或由多晶硅或单晶硅制成。
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| DE102012103578A1 (de) * | 2012-04-24 | 2013-10-24 | Von Ardenne Anlagentechnik Gmbh | Verfahren zur Herstellung einer Dünnschichtsolarzelle |
| US9677168B2 (en) | 2013-10-08 | 2017-06-13 | TPK America, LLC | Touch panel and method for manufacturing the same |
| US20150287843A1 (en) * | 2014-04-03 | 2015-10-08 | Tsmc Solar Ltd. | Solar cell with dielectric layer |
| WO2016042072A1 (en) * | 2014-09-17 | 2016-03-24 | Oerlikon Surface Solutions Ag, Trübbach | Method for producing a double-layer coated cutting tool with improved wear resistance |
| US20170159169A1 (en) * | 2015-12-02 | 2017-06-08 | Ming Chi University Of Technology | Process for manufacturing nickel oxide films with high conductivity |
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| CN1826423A (zh) * | 2003-05-23 | 2006-08-30 | 希莫菲克斯公司 | 透明导电氧化物 |
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| EP0104164A1 (en) * | 1982-03-30 | 1984-04-04 | Nicator Aktiebolag | Method of and apparatus for straightening a deformed frame element of a vehicle body |
| DE3700633C2 (de) * | 1987-01-12 | 1997-02-20 | Reinar Dr Gruen | Verfahren und Vorrichtung zum schonenden Beschichten elektrisch leitender Gegenstände mittels Plasma |
| JP2578815B2 (ja) * | 1987-07-08 | 1997-02-05 | 松下電器産業株式会社 | 直流スパッタリング法 |
| JP2904018B2 (ja) * | 1993-07-28 | 1999-06-14 | 旭硝子株式会社 | 透明電導膜の製造方法 |
| DE69426003T2 (de) * | 1993-07-28 | 2001-05-17 | Asahi Glass Co. Ltd., Tokio/Tokyo | Verfahren und Vorrichtung zur Kathodenzerstäubung |
| DE69418542T2 (de) * | 1993-07-28 | 1999-09-16 | Asahi Glass Co. Ltd., Tokio/Tokyo | Verfahren zur Herstellung funktioneller Beschichtungen |
| JP3249407B2 (ja) * | 1996-10-25 | 2002-01-21 | 昭和シェル石油株式会社 | カルコパイライト系多元化合物半導体薄膜光吸収層からなる薄膜太陽電池 |
| US20020084455A1 (en) * | 1999-03-30 | 2002-07-04 | Jeffery T. Cheung | Transparent and conductive zinc oxide film with low growth temperature |
| US6822158B2 (en) * | 2002-03-11 | 2004-11-23 | Sharp Kabushiki Kaisha | Thin-film solar cell and manufacture method therefor |
| JP2004010753A (ja) | 2002-06-06 | 2004-01-15 | Konica Minolta Holdings Inc | 透明導電性フィルムの製造方法及び透明導電性フィルム |
| US20040112735A1 (en) * | 2002-12-17 | 2004-06-17 | Applied Materials, Inc. | Pulsed magnetron for sputter deposition |
| US20050056312A1 (en) * | 2003-03-14 | 2005-03-17 | Young David L. | Bifacial structure for tandem solar cells |
| SE0303136D0 (sv) * | 2003-11-24 | 2003-11-24 | Chemfilt R & D Ab | Method and apparatus for reactive soilid-gas-plasma deposition |
| DE102006061324B4 (de) * | 2006-06-20 | 2008-07-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Regelung eines reaktiven Hochleistungs-Puls-Magnetronsputterprozesses und Vorrichtung hierzu |
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- 2007-09-28 EP EP07818560A patent/EP2066824B1/de active Active
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| CN1826423A (zh) * | 2003-05-23 | 2006-08-30 | 希莫菲克斯公司 | 透明导电氧化物 |
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| JP5398003B2 (ja) | 2014-01-29 |
| EP2066824A1 (de) | 2009-06-10 |
| WO2008040502A1 (de) | 2008-04-10 |
| EP2066824B1 (de) | 2011-12-28 |
| KR20090063263A (ko) | 2009-06-17 |
| ATE539178T1 (de) | 2012-01-15 |
| US20100006426A1 (en) | 2010-01-14 |
| KR101274857B1 (ko) | 2013-06-13 |
| DE102006046312A1 (de) | 2008-04-03 |
| CN101517122A (zh) | 2009-08-26 |
| JP2010505255A (ja) | 2010-02-18 |
| DE102006046312B4 (de) | 2010-01-28 |
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