CN102803173A - 用具有改善的机械强度的层涂布的玻璃基材 - Google Patents

用具有改善的机械强度的层涂布的玻璃基材 Download PDF

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CN102803173A
CN102803173A CN2011800149063A CN201180014906A CN102803173A CN 102803173 A CN102803173 A CN 102803173A CN 2011800149063 A CN2011800149063 A CN 2011800149063A CN 201180014906 A CN201180014906 A CN 201180014906A CN 102803173 A CN102803173 A CN 102803173A
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oxynitride
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S·奥夫雷
C·布里凯
B·库恩
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Abstract

本发明涉及透明玻璃基材，其与能够构成光伏组件电极的透明导电层结合，由掺杂的氧化物构成，该基材的特征在于在玻璃基材和透明导电层之间，插入一个或多个具有对玻璃的良好附着性能的第一氮化物或氧氮化物、或氧化物或氧碳化物的层，而后是具有对玻璃良好附着性能的一个或多个第二氮化物或氧氮化物、或氧化物或氧碳化物的混合层，以及一个或多个第三氮化物或氧氮化物、或氧化物或氧碳化物的混合层，其能够任选在掺杂状态下构成透明导电层。本发明还涉及制造所述基材的方法，涉及包含所述基材的光伏组件、成形电加热玻璃、等离子屏、平板灯电极和低发射率玻璃。

Description

用具有改善的机械强度的层涂布的玻璃基材
本发明涉及光伏组件的正面基材，特别是透明玻璃基材，还涉及包含所述基材的光伏组件。
在光伏组件中，含有在入射辐射的作用下产生电能的光伏材料的光伏系统位于背面基材和正面基材之间，所述正面基材是入射辐射在达到光伏材料之前穿过的第一个基材。
光伏材料被理解为吸收剂，其例如由以碲化镉、非晶硅、微晶硅或三元黄铜矿组成，所述三元黄铜矿通常含有铜、铟和硒。所述吸收剂层被称为CISe2层。吸收剂层还可以含有镓(例如Cu(In,Ga)Se2或CuGaSe2)、铝(例如Cu(In,Al)Se2)或硫(例如CuIn(Se,S))。其通常表示为术语黄铜矿吸附剂层。
在光伏电池中，当入射辐射到达的主方向被认为是经过顶部时，在转向光伏材料的主表面之下，正面基材通常包含透明电极涂层，其与位于其下的光伏材料电接触。
在本发明的上下文中，术语“光伏电池”应当被理解为通过太阳辐射转换在其电极间产生电流的成分的任何组装，无论所述组装的尺寸以及无论电压和产生的电流的强度，特别是无论所述成分的组装具有一个或多个内部电连接(串联和/或并联)。本发明的上下文中的概念“光伏电池”因此在此等价于概念“光伏组件”或“光伏板”。
本发明涉及玻璃基材上的具有巨大优势的透明导电层，特别是基于氧化物的透明导电层。
因而，其实例为用锡掺杂的氧化铟ITO(铟锡氧化物)层、用氟掺杂的氧化锡的SnO2:F层。所述层构成特定应用的电极，所述特定应用为：平板灯、电致发光玻璃、电致变色玻璃、液晶显示屏、等离子体屏、光伏板或组件、电加热玻璃。在用于低发射系数玻璃的应用中，例如，所述透明导电层不必处于电压下。
在现有技术中，所述透明导电层通常与子层结合，以改善玻璃基材上的透明导电层或堆叠的透明导电层的光学性质。无需穷尽，尤其可以提及PPG的EP611733，其提出氧化硅和氧化锡的混合梯度层，以防止由氟掺杂氧化锡的透明导电层引发的晕彩效果。Roy Gordon的专利FR 2419335也提出所述子层的变体，以改善氟掺杂氧化锡的透明导电层的色彩性能。在所述专利中引用的前体在另一方面不能用在工业规模上。还可以提及Pilkington的专利EP0275662B1，其提出由氧碳化硅构成的子层，其在基于氟掺杂氧化锡的导电层之下，所述子层提供两种作用：防止碱金属从玻璃中扩散的屏蔽层，以及中和反射中的色彩的抗晕彩层。SAINT-GOBAIN也掌握所述领域中的专门技术：因而专利FR2736632提出氧化硅和氧化锡的混合反向指数-梯度子层作为抗变色子层，用于氟掺杂氧化锡的透明导电层。
另一方面，已经观察到，玻璃上的透明导电氧化层具有在光伏组件或所有在先提及的活性应用中分层的趋势。层的分层被理解为其对玻璃的附着性能的丧失。这可以通过裂纹的形成而观察到，所述裂纹可以被本领域内的技术人员轻易地检测。裂纹扩展可以导致层的分离，从而消除了应用的功能性。
开发了老化试验以加速发现所述现象。对于可变时间，其包含将玻璃及其电极处于电场作用中。所述测试的目的是迫使碱金属从玻璃中向层扩散，这是导致出现分层的原因之一。分层测试以下述方式进行。首先，在具有导电电极侧的相对面上，例如基于银的反电极沉积于玻璃上。其次，将如此形成的组装通过与电炉上的基于银的表面直接接触，或者通过在烘箱中退化而达到200℃。一旦达到热平衡，在导电电极上施加约-200V的电势，基于银的反电极接地。这导致电场形成，其诱导碱金属从玻璃向导电层迁移。实施所述测试不同的时间，从一分钟到约约20分钟，这样，依据标准温度和标准压力条件下的玻璃的电阻值，例如得到0.1-40mC/cm2或更大的电荷迁移。观察所述迁移电荷的下限，从出现分层时开始。所述分层也可以用现有技术中提及的子层观察。
为了解决位于玻璃基材上的透明导电氧化层的分层问题，本发明人已经开发了将玻璃基材加入到透明导电氧化层的堆叠的子层，其显著改善玻璃基材的附着性能，尤其在将组装置于电场和相当高的温度下的条件下，所述温度高于100℃，或甚至200℃。
因此，本发明的一个目标是透明玻璃基材，与可以构成光伏组件电极的透明导电层结合，由掺杂的氧化物构成，特征在于在玻璃基材和透明导电层之间，插入一个或多个具有对玻璃的良好附着性能的第一氮化物或氧氮化物、或氧化物或氧碳化物的层，而后是具有对玻璃良好附着性能的一个或多个第二氮化物或氧氮化物、或氧化物或氧碳化物的混合层，以及一个或多个第三氮化物或氧氮化物、或氧化物或氧碳化物的混合层，其可以任选在掺杂状态下是透明导电层。
因此，本发明可以得到在若干方面适于光伏组件的层的堆叠。
玻璃基材上的机械强度在电场存在下不会受不利影响，其起源可以与向光伏组件上施加电压或围绕组件的金属框架的存在内部或外部联系，其电势可以波动，在实际户外阳光暴晒条件下使用。在此参考的太阳光谱是通过ASTM标准确定的AM1.5的太阳光谱。对于大型玻璃表面(全宽度浮法，法国PLF)，可以得到所述显著改善，因为与所述尺寸兼容的沉积过程可以用于讨论的层。
而且，诸如使用比浊计测定的漫透射和浊度的局部变化的审美缺陷可以被解决，从而本发明非常特别地适于光伏组件的制造。
有利地，在24小时中受到用至少100V，优选200V的电场，以及在至少200℃的温度下在基材的任一侧上的处理，不会对本发明的基材的机械强度产生负面影响，依据在测试温度下的玻璃基材的电阻值产生至少2mC/cm2的电荷迁移，优选4mC/cm2。机械强度被理解为堆叠或一部分堆叠不会分层。
优选的，
●所述第一和第二氮化物或氧氮化物，或氧化物或氧碳化物选自Si、Al和Ti的氮化物或氧氮化物，或氧化物或氧碳化物，特别是SiOC、SiO2、SiON、TiO2、TiN和Al2O3；
●所述第三氮化物或氧氮化物，或氧化物或氧碳化物选自Sn、Zn和In的氮化物或氧氮化物，或氧化物或氧碳化物，特别是SnO2、ZnO和InO；
●所述透明导电层由Sn、Zn或In的掺杂氧化物组成，如SnO2:F、SnO2:Sb、ZnO:Al、ZnO:Ga、ZnO:B、InO:Sn或ZnO:In。
依据提供基材的机械强度和期望光学性质的最优组合的实施方案，
●所述一个或多个第一氮化物或氧氮化物，或氧化物或氧碳化物层是氧碳化硅SiOC层；
●所述混合层是硅锡氧化物的层。
●在所述混合层中，[Si]/[Sn]摩尔比至少等于1，优选2；本发明人注意到，所述特征对上述机械强度具有非常特别正面的影响，特别在用作光伏组件的上下文中；
●所述一个或多个第一氮化物或氧氮化物，或氧化物或氧碳化物层的厚度至少等于5nm；
●所述一个或多个第一氮化物或氧氮化物，或氧化物或氧碳化物层的厚度至多等于80nm；实际上，从例如机械强度的观点上出发，更大的厚度不会提供进一步的优势；
●所述混合层的厚度至少等于3nm；
●所述混合层的厚度至多等于65nm，优选40nm；对于更大的厚度，可以出现浊度的局部变化，这在或多或少的程度上对最终产品，尤其是光伏组件的美学外观产生负面影响。
●所述由掺杂氧化物构成的透明导电层与所述混合层通过插入相同的未掺杂氧化物层而连接，未掺杂氧化物和掺杂氧化物的两个层的组合厚度特别为300-1600nm，优选至多等于1100nm，特别优选900nm，两层的厚度比为1:4-4:1。
本发明的另一个目标是用于制造上述基材的方法，通过连续化学汽相沉积，得到所述一个或多个第一氮化物或氧氮化物，或氧化物或氧碳化物层，所述混合层以及所述透明导电层。
在工业规模上，化学汽相沉积(CVD)可以容易地在大型玻璃表面上实施，特别是在全宽度浮法玻璃(法国，PLF)。无需真空装置。
可以提及以下：
●作为SiO2前体(SiOC-SiOSn)：四乙氧基硅烷(TEOS)、六甲基二硅氧烷(HMDSO)、硅烷(SiH4)；
●作为SnO2前体(SiOSn、SnO2、SnO2:F)：单丁基三氯化锡(MBTCl)、二丁基二醋酸锡(DBTA)、四氯化锡(SnCl4)；二丁基二氯化锡(DBTCl)；
●作为其他碳基前体(SiOC)：乙烯、二氧化碳；
●作为其他氧基前体(SiOC、SiOSn、SnO2、SnO2:F)：二氧化碳、氧、水；
●作为氟基前体(SnO2:F)：四氟甲烷(CF4)、八氟丙烷(C3F8)、六氟乙烷(C2F6)、氟化氢(HF)、二氟一氯甲烷(CHClF2)、二氟一氯乙烷(CH3CClF2)、三氟甲烷(CHF3)、二氯二氟甲烷(CF2Cl2)、三氟氯甲烷(CF3Cl)、三氟溴甲烷(CF3Br)、三氟乙酸(TFA，CF3COOH)、三氟化氮(NF3)。
所述连续沉积在至少等于500℃的基材温度下有利地实施，可以达到650℃或更高的值。
例如，SiOC层可以在玻璃基材生产线上沉积，而SiOSn层在所述生产线外侧沉积，或可选的，所述两个层都可以在所述生产线的外侧沉积。
然而，依据本方法的一个优选实施方案，所述连续化学汽相沉积在玻璃基材生产线上实施，例如在包含退火炉的浮法、出口和起点的部分中的连续带上。
而且，本发明的其他目标为：
●包含上述基材的光伏组件；
●包含前述基材的成形电加热玻璃；
●包含依据本发明的基材的等离子屏(用于等离子显示板，简称PDP)；
●包含所述基材的平板灯电极；和
●包含所述基材的低发射系数(low-e)玻璃。
本发明将通过下列实施例详细描述。
对比实施例1
在所有下列实施例中，通过化学汽相沉积将多个层沉积在5cm×5cm×3.2mm的钠钙浮法玻璃样品上。将样品加热到600℃。
在余下的实施例中指出的比例是摩尔百分比。
在此由下列组分起始沉积25nm的SiOC层：
7.8%的SiH4；
26.6%的C2H4；
47.8%的N2；和
17.7%的CO2。
而后，由下列组分起始沉积1μm的SnO2:F层：
3.63%的单正丁基三氯化锡(MBTCl)；
0.45%的三氟乙酸(TFA)；
20%的水；
57%的N2；和
19%的O2。
在所有实施例中，在样品的任一一侧上，样品处于200V的电压，以及200℃的温度下可变的时间。在所述操作后24h，观察分层的迁移电荷的下限值。(参见所述老化测试的上述详细描述)。
所述下限值在此小于0.5mC/cm2，这被认为对应相当低的机械强度，对于许多应用而言是不足的，特别是光伏组件。
而且，未能观察到浊度的基本局部变化。
对比实施例2
由以下组分开始沉积40nm的SiOSn层：
0.08%的MBTCl；
0.04%的四乙氧基硅烷(TEOS)；
0.17%的水；
93.1%的N2；和
6.6%的O2。
所述层的Si/Sn摩尔比为0.5。
其次，如实施例1那样沉积1μm的SnO2:F层。
从小于0.5mC/cm2的迁移电荷值开始观察到分层，这是不足的。
而且所述样品显示对产品的美学外观起负面影响的浊度的局部变化。
实施例3
沉积以下组分：
●25nm的如实施例1的SiOC层；
●40nm的如实施例2的SiOSn层(Si/Sn摩尔比为0.5)；和
●1μm的如前述实施例中的SnO2:F层。
从小于1mC/cm2的迁移电荷值开始观察到分层，这相对于前述实施例的那些而言基本上得到改善，但是在特定要求的应用中仍可以是不足的。
没有观察到浊度的局部变化。
实施例4
沉积以下组分：
●25nm的如实施例3的SiOC层；
●40nm的SiOSn层，Si/Sn摩尔比为1.4，由下列组分起始：
0.08%的MBTCl；
0.11%的TEOS；
0.17%的水；
93%的N2；和
6.6%的O2；和
●如实施例3中的SnO2:F层。
从4-5mC/cm2的迁移电荷值开始出现分层，其足以用于许多需要的应用。
没有观察到浊度的局部变化。
实施例5
重复实施例4，仅改变SiOSn层，在此其Si/Sn摩尔比为2.7，由下列组分得到：
0.08%的MBTCl；
0.23%的TEOS；
0.17%的水；
92.9%的N2；和
6.6%的O2。
从10mC/cm2的迁移电荷值开始出现分层，这是非常好的。
没有观察到浊度的局部变化。
实施例6
重复实施例3-5，改变SiOSn层，厚度为80nm，Si/Sn摩尔比为2.7，所述层由下列组分得到：
0.14%的MBTCl；
0.37%的TEOS；
0.26%的水；
86.8%的N2；和
12.4%的O2。
从15mC/cm2的迁移电荷值开始出现分层，这是非常好的。
然而，观察到浊度的局部变化。
实施例7
重复实施例6，但是SiOSn层的Si/Sn摩尔比为0.5，由下列组分得到：
0.14%的MBTCl；
0.07%的TEOS；
0.26%的水；
87.1%的N2；和
12.4%的O2。
从小于1mC/cm2的迁移电荷值开始出现分层，依据应用，这可以适用或不可以适用，但是其相对是低的。
观察到浊度的局部变化。因此相应的，如实施例6，可以解释为相当大的SiOSn层厚度(80nm)。
实施例8
沉积以下组分：
●由以下组分得到50nm的SiOC层：
10.2%的SiH4；
35%的C2H4；
31.5%的N2；和
23.3%的CO2；
●20nm的SiOSn层，Si/Sn摩尔比为0.6，由下列组分得到：
0.04%的MBTCl；
0.02%的TEOS；
0.11%的水；
96.2%的N2；和
●3.6%的O2；和
●与前述实施例相同的SnO2:F层。
从小于2mC/cm2的迁移电荷值开始出现分层，这在特定应用中是足够的，但是可以改善。
未观察到浊度的局部变化。
实施例9
重复实施例8，仅改变SiOSn层，此时厚度为50nm，Si/Sn摩尔比为2.7，由下列组分得到：
0.10%的MBTCl；
0.27%的TEOS；
0.22%的水；
91.3%的N2；和
8.1%的O2。
在此，产生分层的迁移电荷下限值高，为12mC/cm2。
未观察到浊度的局部变化。
实施例10
重复实施例8和9，仅改变SiOSn层，此时厚度为70nm，Si/Sn摩尔比为2.7，所述层由下列组分得到：
0.13%的MBTCl；
0.37%的TEOS；
0.31%的水；
88.1%的N2；和
11.1%的O2。
在此，观察到分层的起始迁移电荷下限值最高，为20mC/cm2。
然而，美学外观受到浊度的局部变化的轻微负面影响，这是由于相当厚的SiOSn层。
因此，本发明制成了可用的层的堆叠，其提供高机械强度和高可调节光学性质，优选适于要求的应用，尤其是光伏材料。所述堆叠当然与得到目前期望的最高程度下的光伏组件的功能性相适应。

Claims (20)

1.透明玻璃基材，其与能够构成光伏组件电极的透明导电层结合，由掺杂的氧化物构成，该基材的特征在于在玻璃基材和透明导电层之间，插入一个或多个具有对玻璃的良好附着性能的第一氮化物或氧氮化物、或氧化物或氧碳化物的层，而后是具有对玻璃良好附着性能的一个或多个第二氮化物或氧氮化物、或氧化物或氧碳化物的混合层，以及一个或多个第三氮化物或氧氮化物、或氧化物或氧碳化物的混合层，其能够任选在掺杂状态下构成透明导电层。
2.如权利要求1所述的基材，特征在于所述第一和第二氮化物或氧氮化物、或氧化物或氧碳化物选自Si、Al和Ti的氮化物或氧氮化物，或氧化物或氧碳化物，特别是SiOC、SiO2、SiON、TiO2、TiN和Al2O3。
3.如任一前述权利要求所述的基材，特征在于所述第三氮化物或氧氮化物、或氧化物或氧碳化物选自Sn、Zn和In的氮化物或氧氮化物，或氧化物或氧碳化物，特别是SnO2、ZnO和InO。
4.如任一前述权利要求所述的基材，特征在于所述透明导电层由Sn、Zn或In的掺杂氧化物构成，所述Sn、Zn或In的掺杂氧化物例如为SnO2:F、SnO2:Sb、ZnO:Al、ZnO:Ga、InO:Sn、ZnO:B或ZnO:In。
5.如任一前述权利要求所述的基材，特征在于所述一个或多个第一氮化物或氧氮化物、或氧化物或氧碳化物的层是氧碳化硅SiOC层。
6.如任一前述权利要求所述的基材，特征在于所述混合层是硅锡氧化物层。
7.如权利要求6所述的基材，特征在于在所述混合层中，[Si]/[Sn]摩尔比至少等于1，优选等于2。
8.如任一前述权利要求所述的基材，特征在于所述一个或多个第一氮化物或氧氮化物、或氧化物或氧碳化物的层的厚度至少等于5nm。
9.如任一前述权利要求所述的基材，特征在于所述一个或多个第一氮化物或氧氮化物、或氧化物或氧碳化物的层的厚度至多等于80nm。
10.如任一前述权利要求所述的基材，特征在于所述混合层的厚度至少等于3nm。
11.如任一前述权利要求所述的基材，特征在于所述混合层的厚度至多等于65nm，优选40nm。
12.如任一前述权利要求所述的基材，特征在于所述由掺杂氧化物构成的透明导电层与所述混合层通过插入相同的未掺杂氧化物层而结合。
13.如权利要求12所述的基材，特征在于未掺杂氧化物和掺杂氧化物的两个层的组合厚度为300-1600nm，优选至多等于1100nm，特别优选900nm，两层的厚度比为1:4-4:1。
14.一种制造如任一前述权利要求所述的基材的方法，特征在于通过连续化学汽相沉积，得到所述一个或多个第一氮化物或氧氮化物、或氧化物或氧碳化物层，所述混合层以及所述透明导电层。
15.如权利要求14所述的方法，特征在于所述沉积在玻璃基材的生产线上进行。
16.一种光伏组件，其包含如权利要求1-13的任一所述的基材。
17.一种成形电加热玻璃，其包含如权利要求1-13的任一所述的基材。
18.一种等离子屏，其包含如权利要求1-13的任一所述的基材。
19.一种平板灯电极，其包含如权利要求1-13的任一所述的基材。
20.一种低发射率玻璃，包含如权利要求1-13的任一所述的基材。
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