CN113097342A - 一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法 - Google Patents

一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法 Download PDF

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CN113097342A
CN113097342A CN202110346301.XA CN202110346301A CN113097342A CN 113097342 A CN113097342 A CN 113097342A CN 202110346301 A CN202110346301 A CN 202110346301A CN 113097342 A CN113097342 A CN 113097342A
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alox
film
layer
passivation
solar cell
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CN113097342B (zh
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黄智�
张�林
张鹏
杨东
徐涛
翟绪锦
谢泰宏
萧圣义
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Tongwei Solar Hefei Co Ltd
Tongwei Solar Jintang Co Ltd
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Tongwei Solar Jintang Co Ltd
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Abstract

本发明公开了一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法，属于太阳能电池制备技术领域。本发明将经热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到100‑2000mtorr的压强下，并将腔体温度加热到300‑400℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜，所述AlOx钝化膜采用两层、三层或多层膜的结构。本发明采用AlOx多层膜，对每层AlOx膜采用NH3和N2O其进行处理，从而整体增加AlOx膜的钝化效果。同时，底层通过低沉积速率和高氧含量的工艺条件，进一步增加了AlOx的负电荷密度，提高了硅片背表面的场钝化效果；外层采用高沉积速率工艺，确保整体工艺时间不受影响。通过本发明提供的技术路线制备的太阳能电池片，转换效率可以提升0.05‑0.10％。

Description

一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法
技术领域
本发明涉及太阳能电池制备技术领域，更具体地说，涉及一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法。
背景技术
晶硅太阳能电池是一种利用PN结的光生伏特效应将光能转换成电能的器件，其中PERC(Passivated Emitter and Rear Cell)太阳能电池最早起源于上世纪八十年代，由澳洲新南威尔士大学的Martin Green研究组开发而成。有别于常规太阳能电池，其在电池背表面采用了介质膜钝化和局域金属接触的技术，使得背表复合速率显著降低、增加电池的背反射，从而大幅提升了电池的长波效应。本世纪初，用于P型PERC电池背面的AlOx介质膜的钝化作用的发现及研究，使得PERC电池的产业化逐步成为可能。随后随着沉积AlOx产业化制备技术和设备的成熟，加上激光技术的引入，PERC技术开始逐步走向产业化。由于工艺简单、成本较低，2017年以后，PERC电池已逐步发展成市场上主流的高效太阳能电池产品和技术。
目前，AlOx钝化层的制备方式主要有原子层沉积(ALD)、等离子体增强原子层沉积(PEALD)、等离子体增强化学气相沉积(PECVD)的方式，物理气相沉积(PVD)用的较少。其中，ALD和PEALD制备原理是先后将氧化铝的前驱体及氧化剂前驱体通入反应腔体，然后通过前驱体在硅片表面上的吸附、反应完成一层原子层尺度的AlOx层制备，如此循环不同次数制备出设定厚度的AlOx钝化层，此处得到的AlOx钝化层是采用同一工艺条件来制备的，所以通常统一称为单层膜。每次循环及一种前驱体吸附后，均需吹扫腔体，去除反应物和多余前驱体。PECVD是一种用等离子体激活反应气体，促进在基体表面或近表面空间进行化学反应，生成固态膜的技术。其基本原理是在高频或直流电场作用下，源气体电离形成等离子体，利用低温等离子体作为能量源，使得AlOx的几种反应气体激活并实现化学气相沉积。
由于管式PECVD技术具备成膜速率高，易维护，Uptime高、工艺灵活以及和氮化硅膜可实现同机台同管制备等特点，具有显著的综合成本优势，逐步成为电池厂商的首选。但是，目前采用PECVD制备AlOx膜的工艺，AlOx膜均为单层膜(ALD、PEALD等方式也一样)。其制备的AlOx膜在表面化学钝化和场钝化的钝化效果方面还存在提升空间，且PECVD制备钝化膜时，对硅片基体存在等离子体的轰击损伤，也破坏了硅片表面的化学钝化效果。所以，如何缩小钝化方面的差异，提高PECVD方式制备的PERC电池片转换效率仍是需要持续改进的问题。
针对PECVD方式制备的AlOx膜在表面化学钝化和场钝化的钝化效果方面存在的问题，专利公布号CN 110767757 A公开了一种高效PERC电池背面氧化铝膜及其制备方法，该申请案公开了一种管式PECVD工艺，包括：(1)采用TMA与N2O在硅片背面进行PECVD沉积，形成氧化铝层；(2)通入NH3引入氢源，进入氧化铝层以及P型硅表层，在P型硅背表面形成高氢介质膜；(3)通入N2O，将未反应的TMA充分反应。该申请案在AlOx膜和SiNx膜之间分步引入NH3和N2O，分别提供H钝化和对未反应完全的TMA进行处理，从而提升整个钝化效果。
专利公布号CN 111192935 A公开了一种管式PERC太阳能电池背钝化结构及其制备方法；该申请案首先在太阳能电池片背面形成氧化铝层；然后在管式PECVD设备中通入含氧混合气体，并采用所述含氧混合气体形成的等离子体对所述氧化铝层进行处理，以提升所述氧化铝层的负电荷密度；最后，在氧化铝层上形成至少一层氮化硅层。该申请案通过采用含氧混合气体对氧化铝钝化层进行处理，提升AlOx膜的负电荷密度从而提升场钝化效果。
上述申请案虽均能在一定程度上提升AlOx膜的场钝化效果，但均存在进一步改善空间。
发明内容
1.发明要解决的技术问题
本发明的目的在于克服现有技术的不足，提供了一种太阳能电池、其AlOx镀膜方法、电池背钝化结构及方法，本发明采用AlOx多层膜，对每层AlOx膜采用NH3和N2O进行处理，从而整体增加AlOx膜的钝化效果。同时，底层通过低沉积速率和高氧含量的工艺条件，进一步增加了AlOx的负电荷密度，提高了硅片背表面的场钝化效果；外层采用高沉积速率工艺，确保整体工艺时间不受影响。通过本发明提供的技术路线制备的太阳能电池片，转换效率可以提升0.05-0.10％。
2.技术方案
为达到上述目的，本发明提供的技术方案为：
本发明的一种太阳能电池的AlOx镀膜方法，将经热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到100-2000mtorr的压强下，并将腔体温度加热到300-400℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜，所述AlOx钝化膜采用两层、三层或多层膜结构，且采用NH3和N2O对每层AlOx膜进行处理。
更进一步地，所述AlOx钝化膜采用两层膜结构且两层膜采用不同沉积速率的工艺条件，具体如下：
底层AlOx膜工艺条件为：笑气流量：3500-4500sccm，TMA流量：30-60sccm；射频功率：4000-6000W；脉冲开关比20：(1000-1500)；工艺时间40-80s；
顶层AlOx膜工艺条件为：笑气流量：2500-3500sccm，TMA流量：50-100sccm；射频功率：6000-8000W；脉冲开关比20：(800-1200)；工艺时间80-150s。
本发明的一种太阳能电池的背钝化方法，其步骤为：
步骤一、采用单插(双面长氧化硅)、正靠正(背面朝外)或背靠背加大氧流量工艺，在硅片基体上制备氧化硅层；
步骤二、采用所述的底层AlOx膜工艺条件制备底层AlOx膜；
步骤三、去除步骤二残余气体后，通入NH3和N2O，对底层AlOx膜进行H钝化和氧化处理；
步骤四、去除步骤三残余气体后，采用所述的顶层AlOx膜工艺条件制备顶层AlOx膜；
步骤五、去除步骤四残余气体后，进行升温同时通入NH3和N2O，对顶层AlOx膜进行H钝化和氧化处理；
步骤六、在腔体升温到400-550℃时，制备氮化硅膜，或氮化硅与氮氧化硅、氧化硅中的一种或多种的复合膜。
更进一步地，步骤一采用背靠背方式，热氧化工艺条件为：温度650-750℃，氧气流量2500-4000sccm，时间20-40min。
更进一步地，步骤三、步骤五所述的对AlOx膜进行H钝化和氧化处理的工艺条件为：NH3和N2O的流量控制在1000-4000sccm，真空压强500-2000mtorr，射频功率：2500-5000W，脉冲开关比30：(100-500)，工艺时间100-300s。
更进一步地，步骤三-步骤五均通过设定0-100mtorr的压强，抽真空20-60s去除残余气体。
本发明的一种太阳能电池的背钝化结构，包括硅片基体、氧化硅层，所述的氧化硅层设置在硅片基体上，所述的氧化硅层上设置AlOx层，该AlOx层采用两层、三层或多层膜的结构。
更进一步地，所述AlOx层优选两层膜结构，其AlOx底层、AlOx顶层采用所述的底层AlOx膜工艺条件、顶层AlOx膜工艺条件制备。
本发明的一种太阳能电池的背钝化结构，该背钝化结构采用所述的背钝化方法制得。
本发明的一种太阳能电池，包括所述的背钝化结构。
3.有益效果
采用本发明提供的技术方案，与已有的公知技术相比，具有如下显著效果：
(1)本发明鉴于现有工艺制备得到的AlOx膜均为较厚的单层膜，对AlOx膜进行处理的深度不够，将AlOx膜拆分为多层膜结构，并在每层AlOx膜后均采用NH3和N2O同时对AlOx膜进行氢化和氧化处理，增加了AlOx膜整体的H钝化效果和负电荷密度引起的场钝化效果。
(2)本发明在镀AlOx钝化膜之前，通过热氧化退火工艺，增加了硅片背面氧化硅的厚度和致密性；同时，AlOx钝化膜采用多层膜方式，底层采用低功率和脉冲开关比工艺，降低了对硅片表面氧化硅的破坏，提升了背面钝化层的表面化学钝化效果。
(3)本发明采用AlOx多层膜，底层通过低沉积速率和高氧含量的工艺条件，增加了AlOx的负电荷密度，提高了硅片背表面的场钝化效果。同时，外层采用高沉积速率工艺，确保了整体工艺时间不受影响。
(4)通过本发明提供的技术路线制备的太阳能电池片，转换效率可以提升0.05-0.10％。
附图说明
图1为本发明的太阳能电池的结构切面图。
示意图中的标号说明：
1、硅片基体；2、氧化硅层；3、AlOx底层；4、AlOx顶层；5、氮化硅复合层。
具体实施方式
为进一步了解本发明的内容，结合附图和实施例对本发明作详细描述。
实施例1
结合图1，本实施例的一种太阳能电池的背钝化结构，包括硅片基体1、氧化硅层2、AlOx层和氮化硅复合层4，所述的氧化硅层2设置在硅片基体1背面，氧化硅层2上设置AlOx层，该AlOx层可采用两层、三层或多层膜结构。各层镀膜工艺条件可以采用一致或不同沉积速率的工艺。
本实施例优选两层膜结构且两层不同沉积速率的工艺条件，具体工艺如下：
将经过热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到100mtorr的压强下并将腔体温度加热到300℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜。
其中，底层(接近硅片表面)AlOx膜工艺条件为：笑气流量：3500sccm，TMA流量：30sccm；射频功率：4000W；脉冲开关比20：1000；工艺时间40s；
顶层(远离硅片表面)AlOx膜工艺条件为：笑气流量：2500sccm，TMA流量：50sccm；射频功率：6000W；脉冲开关比20：800；工艺时间80s。
实施例2
本实施例的一种太阳能电池的背钝化结构，基本同实施例1，其不同之处在于：本实施例的AlOx镀膜工艺条件，如下：
将经过热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到2000mtorr的压强下并将腔体温度加热到400℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜。
其中，底层(接近硅片表面)AlOx膜工艺条件为：笑气流量：4500sccm，TMA流量：60sccm；射频功率：6000W；脉冲开关比20：1500；工艺时间80s；
顶层(远离硅片表面)AlOx膜工艺条件为：笑气流量：3500sccm，TMA流量：100sccm；射频功率：8000W；脉冲开关比20：1200；工艺时间150s。
实施例3
本实施例的一种太阳能电池的背钝化结构，基本同实施例1，其不同之处在于：本实施例的AlOx镀膜工艺条件，如下：
将经过热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到1000mtorr的压强下并将腔体温度加热到340℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜。
其中，底层(接近硅片表面)AlOx膜工艺条件为：笑气流量：4000sccm，TMA流量：50sccm；射频功率：5000W；脉冲开关比20：1200；工艺时间60s；
顶层(远离硅片表面)AlOx膜工艺条件为：笑气流量：3000sccm，TMA流量：80sccm；射频功率：7000W；脉冲开关比20：1000；工艺时间120s。
实施例4
本实施例的一种太阳能电池的背钝化结构，基本同实施例1，其不同之处在于：本实施例太阳能电池的背钝化过程如下：
1.热氧化退火
采用单插(双面长氧化硅)方式，在碱抛工艺后的硅片上双面制备氧化硅，热氧化工艺在700℃下，氧气流量3000sccm，时间25min。
2.底层AlOx膜制备
将经过热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到1000mtorr的压强下并将腔体温度加热到350℃后，制备底层AlOx，工艺条件为：笑气流量4000sccm，TMA流量50sccm，射频功率5000W，脉冲开关比20：1400，工艺时间60s。
3.抽真空
完成底层AlOx膜制备后，设定100mtorr的压强，抽真空60s去除残余气体。
4.底层AlOx膜氢化和氧化处理
完成残余气体去除后，通入NH3流量3000sccm和N2O流量3000sccm，真空压强1000mtorr，射频功率：4000W，脉冲开关比30：200，工艺时间250s。对底层AlOx膜进行H钝化和氧化处理。
5.抽真空
完成底层AlOx膜氢化和氧化处理，设定100mtorr的压强，抽真空60s去除残余气体。
6.顶层AlOx制备
完成以上步骤后，制备顶层AlOx膜，工艺条件为：笑气流量3000sccm，TMA流量80sccm，射频功率7000W，脉冲开关比20：1000，工艺时间100s；
7.抽真空
完成顶层AlOx膜氢化和氧化处理，设定100mtorr的压强，抽真空60s去除残余气体。
8.顶层AlOx膜氢化和氧化处理
完成残余气体去除后，通入NH3流量3000sccm和N2O流量3000sccm，真空压强1000mtorr，射频功率：4000W，脉冲开关比30：200，工艺时间250s。对顶层AlOx膜进行H钝化和氧化处理。
9.氮化硅复合膜
在腔体升温到480℃时，制备氮化硅或氮化硅膜，与氮氧化硅、氧化硅中的一种或多种的复合膜。
实施例5
本实施例的多层AlOx背钝化工艺，具体如下：
1.热氧化退火：采用背靠背加大氧流量工艺，增加硅片背面氧化硅的厚度和致密性。热氧化采用650℃，氧气流量2500sccm，时间20min。
2.底层AlOx膜：采用实施例2所述PECVD方式制备底层AlOx的钝化膜，其中底层采用低功率，低脉冲开关比的底沉积速率镀膜工艺条件。
3.抽真空：完成底层AlOx膜制备后，设定50mtorr的压强，抽真空20s去除残余气体。
4.底层AlOx膜氢化和氧化处理：完成残余气体去除后，同时通入NH3和N2O，流量在1000sccm，真空压强500mtorr，射频功率：2500W，脉冲开关比30：100-500，工艺时间100s。对底层AlOx膜进行H钝化和氧化处理。
5.抽真空：完成对底层AlOx膜氢化和氧化处理后，设定50mtorr的压强，抽真空20s去除残余气体。
6.顶层AlOx膜：采用实施例2所述PECVD方式制备顶层AlOx的钝化膜，其中顶层采用高功率，高脉冲开关比的高沉积速率镀膜工艺条件。
7.抽真空：完成对顶层AlOx膜制备后，设定50mtorr的压强，抽真空20s去除残余气体。同时进行升温。
8.顶层AlOx膜氢化和氧化处理：完成残余气体去除后，同时通入NH3和N2O，流量在1000sccm，真空压强500mtorr，射频功率：2500W，脉冲开关比30：100，工艺时间100s。对顶层AlOx膜进行H钝化和氧化处理。
9.氮化硅复合膜：在腔体升温到400℃时，制备氮化硅膜，或氮化硅与氮氧化硅、氧化硅中的一种或多种的复合膜。
实施例6
本实施例的太阳能电池，其可采用如实施例1-5任一的背钝化结构。
实施例1-6所述的方案，鉴于现有工艺制备得到的AlOx膜均为较厚的单层膜，对AlOx膜进行处理的深度不够，将AlOx膜拆分为多层膜结构，并在每层AlOx膜后均采用NH3和N2O同时对AlOx膜进行氢化和氧化处理，增加了AlOx膜整体的H钝化效果和负电荷密度引起的场钝化效果。采用AlOx多层膜，底层通过低沉积速率和高氧含量的工艺条件，增加了AlOx的负电荷密度，提高了硅片背表面的场钝化效果。同时，外层采用高沉积速率工艺，确保了整体工艺时间不受影响。在镀AlOx钝化膜之前，通过热氧化退火工艺，增加了硅片背面氧化硅的厚度和致密性；同时，AlOx钝化膜底层采用低功率和脉冲开关比工艺，降低了对硅片表面氧化硅的破坏，提升了背面钝化层的表面化学钝化效果。PERC电池片转换效率可以提升0.05-0.10％。
以上示意性的对本发明及其实施方式进行了描述，该描述没有限制性，附图中所示的也只是本发明的实施方式之一，实际的结构并不局限于此。所以，如果本领域的普通技术人员受其启示，在不脱离本发明创造宗旨的情况下，不经创造性的设计出与该技术方案相似的结构方式及实施例，均应属于本发明的保护范围。

Claims (10)

1.一种太阳能电池的AlOx镀膜方法，其特征在于：将经热氧化退火后的硅片置入管式PECVD设备中，将腔体抽真空到100-2000mtorr的压强下，并将腔体温度加热到300-400℃后，通入笑气和TMA的反应气体，打开射频电源制备AlOx钝化膜，所述AlOx钝化膜采用两层、三层或多层膜结构，且采用NH3和N2O对每层AlOx膜进行处理。
2.根据权利要求1所述的一种太阳能电池的AlOx镀膜方法，其特征在于：所述AlOx钝化膜采用两层膜结构且两层膜采用不同沉积速率的工艺条件，具体如下：
底层AlOx膜工艺条件为：笑气流量：3500-4500sccm，TMA流量：30-60sccm；射频功率：4000-6000W；脉冲开关比20：(1000-1500)；工艺时间40-80s；
顶层AlOx膜工艺条件为：笑气流量：2500-3500sccm，TMA流量：50-100sccm；射频功率：6000-8000W；脉冲开关比20：(800-1200)；工艺时间80-150s。
3.一种太阳能电池的背钝化方法，其特征在于，其步骤为：
步骤一、采用单插、正靠正或背靠背加大氧流量工艺，在硅片基体上制备氧化硅层；
步骤二、采用如权利要求2所述的底层AlOx膜工艺条件制备底层AlOx膜；
步骤三、去除步骤二残余气体后，通入NH3和N2O，对底层AlOx膜进行H钝化和氧化处理；
步骤四、去除步骤三残余气体后，采用如权利要求2所述的顶层AlOx膜工艺条件制备顶层AlOx膜；
步骤五、去除步骤四残余气体后，进行升温同时通入NH3和N2O，对顶层AlOx膜进行H钝化和氧化处理；
步骤六、在腔体升温到400-550℃时，制备氮化硅膜，或氮化硅与氮氧化硅、氧化硅中的一种或多种的复合膜。
4.根据权利要求3所述的一种太阳能电池的背钝化方法，其特征在于：步骤一采用背靠背方式，热氧化工艺条件为：温度650-750℃，氧气流量2500-4000sccm，时间20-40min。
5.根据权利要求3或4所述的一种太阳能电池的背钝化方法，其特征在于：步骤三、步骤五所述的对AlOx膜进行H钝化和氧化处理的工艺条件为：NH3和N2O的流量控制在1000-4000sccm，真空压强500-2000mtorr，射频功率：2500-5000W，脉冲开关比30：(100-500)，工艺时间100-300s。
6.根据权利要求5所述的一种太阳能电池的背钝化方法，其特征在于：步骤三-步骤五均通过设定0-100mtorr的压强，抽真空20-60s去除残余气体。
7.一种太阳能电池的背钝化结构，包括硅片基体(1)、氧化硅层(2)，所述的氧化硅层(2)设置在硅片基体(1)上，其特征在于：所述的氧化硅层(2)上设置AlOx层，该AlOx层采用两层、三层或多层膜的结构。
8.根据权利要求7所述的一种太阳能电池的背钝化结构，其特征在于：所述AlOx层优选两层膜结构，其AlOx底层(3)、AlOx顶层(4)采用如权利要求2所述的工艺条件制备。
9.一种太阳能电池的背钝化结构，其特征在于：该背钝化结构采用如权利要求3-6任一项所述的背钝化方法制得。
10.一种太阳能电池，其特征在于：包括如权利要求7-9任一项所述的背钝化结构。
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