CN109182971A - 一种利用反应等离子沉积技术生长宽光谱mgzo-tco薄膜的方法及应用 - Google Patents
一种利用反应等离子沉积技术生长宽光谱mgzo-tco薄膜的方法及应用 Download PDFInfo
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Abstract
一种利用反应等离子沉积技术生长宽光谱MGZO‑TCO薄膜的方法及其应用，属于光电子器件领域。以组分纯度为99.99％的MgO和Ga2O3掺杂的ZnO靶材即ZnO:Ga2O3:MgO陶瓷靶作为靶材原料，溅射气体为Ar气，镀膜过程中引入少量H2或O2，基片偏压0‑150V；衬底温度为室温‑200度，得到结构为glass/MGZO薄膜。器件界面生长缓冲层SnOx，获得复合结构SnOx/MGZO薄膜。本发明薄膜具有宽光谱透过率，并且维持优良的电学特性和表面结构，应用于晶硅异质结太阳电池器件，可提高晶体硅异质结太阳电池等器件效率。
Description
技术领域
本发明属于光电子器件(如太阳电池)领域，特别是一种反应等离子体沉积室温生长宽光谱MGZO透明导电薄膜及太阳电池(如硅基和CIGS等器件)应用。
背景技术
透明导电氧化物(transparent conductive oxide-TCO)薄膜材料是太阳电池的重要组成部分，参见文献：A.V.Shah,H.Schade,M.Vanecek,et al.Progress inPhotovoltaics 12(2004)113-142、J.Müller,B.Rech,J.Springer,et al.Solar Energy77(2004)917-930。当前薄膜电池中应用最为广泛的TCO薄膜是F掺杂SnO2薄膜(SnO2:F)和Sn掺杂In2O3薄膜(In2O3:Sn)。F掺杂SnO2(FTO)薄膜通常是利用常压CVD(APCVD)技术制备，生长温度较高(～500℃)，这对于低温沉积和强H等离子体环境中生长的材料而言，将限制其进一步应用，参见文献：S.Major,S.Kumar,M.Bhatnagar,et al.Applied Physics Letters49(1986)394-396。Sn掺杂In2O3(ITO)薄膜由于In的成本较高，并且在强H等离子体环境中性能容易恶化，也限制了其在太阳电池中的广泛应用。相比于其他TCO薄膜材料，ZnO薄膜具有源材料丰富，无毒且相对生长温度低(室温-300℃)和在强H等离子体环境中性能稳定等特点获得了广泛研究和应用。
ZnO-TCO薄膜在多种光电器件(如太阳电池，发光二极管等)中扮演着重要的角色。硅基太阳电池如晶硅异质结太阳电池(SHJ)和CIGS太阳电池是具有重要商业应用价值的研究课题，其顶部需要透明导电层需要较好的导电性和良好的透过率，以获得高效率电池。对于太阳电池方面的应用来说，TCO可作为硅异质结太阳电池，硅基薄膜太阳电池、铜铟镓硒薄膜太阳电池和碲化镉薄膜太阳电池的透明电极和反射层。考虑到本征氧化锌较差的导电性能，III族元素例如B，Ga，Al等作为掺杂剂改善本征ZnO的光电属性。在众多掺杂剂中，Ga离子与Zn离子半径相似，从而在掺杂时造成较少的晶格失配，并且替位的Ga离子能够作为施主改善薄膜的电学性能。
作为硅异质结太阳电池或CIGS等窗口电极层，TCO应该在约320-1200nm有很高的透过率，对于传统的Ga掺杂ZnO即GZO或者Al掺杂ZnO即AZO来说，很难平衡近红外(NIR)与近紫外(NUV)的透过率。当载流子浓度提高，由于B-M效应造成带隙展宽获得更好的NUV透过率时，由于高的载流子浓度增加载流子的吸收因而导致了NIR透过率的减小。为了能够解决这种矛盾，由于MgO具有较宽的带隙(～7.8eV)，考虑引入Mg作为一种掺杂剂。许多研究已经报道通过Mg的引入，ZnO的带隙可以从3.3eV调节增加到7.8eV，参考文献：S.H.Jang,S.F.Chichibu,.Structural,elastic,and polarization parameters and bandstructures of wurtzite ZnO and MgO,Journal ofApplied Physics,2012,112:073503-073506；X.Gu,L.Zhu,Z.Ye,et al.Highly transparent and conductive Zn0.85Mg0.15O:Althin films prepared by pulsed laser deposition,Solar Energy Materials andSolar Cells,2008,92:343-347；S.W.Shin,I.Y.Kim,G.H.Lee,et al,Design and growthof quaternary Mg and Ga codoped ZnO thin films with transparent conductivecharacteristics,Crystal Growth&Design,2011,11:4819-4824。这样既展宽了带隙，又不会因为高的载流子减少了近红外边的透过率，这将同时改善近红外和近紫外的透过率。因此，这将有利于改善硅基太阳电池的量子效率。适当的Mg和Ga共同引入ZnO中能够同时改善NUV和NIR透过率并保证优良的电学性能。此外，引入氢气能够改善ZnO薄膜的电学性能，参考文献：Y.R.Park,J.Kim,Y.S.Kim,.Effect ofhydrogen doping in ZnO thin films bypulsed DC magnetron sputtering,Applied Surface Science,2009,255:9010-9014.)，H能够作为浅施主改善薄膜的特性，参见文献：Chris G.Van de Walle.Hydrogen as aCause of Doping in Zinc Oxide,Physical Review Letters 85(2000)1012-1015。
生长ZnO-TCO薄膜方法很多，有磁控溅射技术，金属有机化学其相沉积技术和溶胶-凝胶技术，反应等离子体沉积技术等。其中反应等离子体沉积具有生长温度低，离子轰击小，高沉积速率和大面积镀膜等优点。
本发明利用反应等离子体沉积技术(RPD)室温生长MgO和Ga2O3掺杂的ZnO-TCO即MGZO薄膜，并获得复合结构SnOx/MGZO，将其应用于硅基太阳电池(如晶硅异质结或CIGS太阳电池)，其中ZnO陶瓷靶材(掺杂剂为MgO和Ga2O3)作为原材料，Ar气体作为溅射气体，同时生长过程中可引入H2气体和O2气体以及基片偏压。上述技术特征区别于当前其他镀膜生长获得的ZnO薄膜的方法。
发明内容
本发明的目的是针对上述技术分析，提供一种用反应等离子沉积(RPD)技术低温(如室温)生长MgO和Ga2O3掺杂的ZnO-TCO即MGZO薄膜并应用于太阳电池(尤其晶硅异质结太阳电池)。本方法解决常规镀膜技术生长ZnO薄膜光学和电学性能差、衬底温度高和对器件材料损伤等缺点，通过RPD技术生长获得离子能量轰击小，宽光谱高透过率和低电阻率MGZO薄膜；并设计了一种超薄缓冲层SnOx，形成复合结构SnOx/MGZO。该发明实现的ZnO-TCO薄膜可应用于太阳电池，有效地提高了器件效率。
本发明的技术方案：
一种利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，以组分纯度为99.99％的MgO和Ga2O3掺杂的ZnO靶材即ZnO:Ga2O3:MgO陶瓷靶作为靶材原料，溅射气体为Ar气，镀膜过程中引入少量H2或O2，基片偏压0-150V；在玻璃衬底上生长MGZO薄膜，衬底温度为室温-200度，得到结构为glass/MGZO薄膜。进一步地，设计并生长超薄SnOx缓冲层，得到复合结构SnOx/MGZO薄膜。
所述的ZnO陶瓷靶中靶材组分Ga2O3的重量百分比均为0.5-2.0％；靶材组分MgO的重量百分比均为1.0-8.0％。
所述的MGZO薄膜厚度为100-2000nm。
所述的气体Ar气的气压为1.0-6.0mTorr；过程中引入氢气的流量为0sccm至10sccm；过程中引入氧气的流量为0sccm至10sccm。
所述的界面缓冲层SnOx的厚度为0.2-8nm。
以上利用反应等离子沉积技术生长宽光谱MGZO薄膜的方法所得薄膜应用于太阳电池器件。
所述的太阳电池器件包括晶硅基异质结太阳电池或CIGS太阳电池。
本发明的优点及效果：相比于利用溅射镀膜技术获得的ZnO-TCO薄膜，本发明反应等离子体沉积(RPD)技术生长的宽光谱MGZO-TCO薄膜具有宽光谱透过率，并且维持优良的电学特性和表面结构。该宽光谱MGZO-TCO薄膜应用于器件，可获得高效率硅基异质结太阳电池等；此外，应用界面缓冲层SnOx形成复合结构SnOx/MGZO薄膜可提高晶体硅异质结太阳电池等器件效率。
附图说明
图1为反应等离子体沉积系统示意图。
图2为MGZO薄膜结构示意图。
图3为MGZO薄膜结构SEM图像。
图4为MGZO薄膜应用于太阳电池的结构示意图。
图5为MGZO薄膜应用于太阳电池的实验J-V性能。
图6为复合结构SnOx(Buffer)/MGZO晶硅异质结太阳电池结构示意图。
表1为复合结构SnOx(Buffer)/MGZO应用于太阳电池实验J-V性能参数。
具体实施方式
实施例1：
1、利用反应等离子体沉积技术，其系统结构示意图如图1。以纯度为99.99％的ZnO陶瓷靶作为靶材原料，陶瓷靶中掺杂剂组分Ga2O3掺杂百分比为1.5％，陶瓷靶中掺杂剂组分MgO掺杂百分比为4.0％；溅射气体为Ar气体，在玻璃衬底上生长MGZO薄膜，衬底温度为室温，薄膜厚度为～480nm。该薄膜结构为glass/MGZO，如图2所示。
图3为该MGZO薄膜SEM图像，薄膜呈现一定的粗糙度2.8nm，并出现类金字塔状晶粒，晶粒尺寸～30-100nm；薄膜致密且具有350-1200较好的透过率85％和导电性10-4数量级欧姆厘米。
2、将该绒面结构ZnO薄膜应用于晶硅异质结太阳电池，图4为晶硅异质结太阳电池结构示意图。首先晶体硅制造绒面并两面分别镀制i-a-Si和p-a-Si以及n-a-Si；而后利用RPD技术室温在晶硅异质结顶部和底部分别镀制MGZO薄膜，最后镀制金属电极Ag/Al和Al电极，上述特征构成太阳电池器件。图5为晶硅异质结太阳电池J-V性能图，该发明实现的MGZO薄膜应用于硅异质结太阳电池，光电效率达19.016％。
实施例2：
1、利用反应等离子体沉积技术，以纯度为99.99％的ZnO陶瓷靶作为靶材原料，陶瓷靶中掺杂剂组分Ga2O3掺杂百分比为1.5％，陶瓷靶中掺杂剂组分MgO掺杂百分比为4.0％；溅射气体为Ar气体，在玻璃衬底上生长MGZO薄膜，衬底温度为室温；超薄缓冲层SnOx设计为～1nm，实现复合结构SnOx/MGZO。
2、图6为该SnOx/MGZO薄膜应用于晶硅异质结太阳电池结构示意图，首先晶体硅制造绒面并两面分别镀制i-a-Si和p-a-Si和n-a-Si；而后电池底部一侧镀制传统TCO薄膜，顶部一侧镀制SnOx/MGZO复合结构薄膜；最后两侧镀制金属电极Ag/Al栅线，上述特征构成太阳电池器件。表1为SnOx/MGZO薄膜应用的晶硅异质结太阳电池J-V性能实验参数。
表1晶硅异质结太阳电池J-V性能参数比较
由表1可知，相比于无缓冲层的太阳电池器件，具有SnOx/MGZO复合薄膜结构的晶体硅异质结太阳电池，其光电转化效率相对提高10.68％。
Claims (10)
1.一种利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：以组分纯度为99.99％的MgO和Ga2O3掺杂的ZnO靶材即ZnO:Ga2O3:MgO陶瓷靶作为靶材原料，溅射气体为Ar气，镀膜过程中引入少量H2或O2，基片偏压0-150V；在玻璃衬底上生长MGZO薄膜，衬底温度为室温-200度，得到结构为glass/MGZO薄膜。
2.根据权利要求1所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：结合超薄SnOx缓冲层，得到复合结构SnOx/MGZO薄膜。
3.根据权利要求1所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：所述ZnO陶瓷靶中靶材组分Ga2O3的重量百分比均为0.5-2.0％；ZnO陶瓷靶中靶材组分MgO的重量百分比均为1.0-8.0％。
4.根据权利要求1所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：所述薄膜厚度为100-2000nm。
5.根据权利要求1所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：气体Ar气的气压为1.0-6.0mTorr；过程中引入氢气的流量为0sccm至10sccm；过程中引入氧气的流量为0sccm至10sccm；衬底温度为室温-200度。
6.根据权利要求2所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法，其特征是：界面缓冲层SnOx的厚度为0.2-8nm。
7.根据权利要求1或2所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法所得薄膜的应用，其特征是：所得薄膜应用于太阳电池器件。
8.根据权利要求7所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法所得薄膜的应用，其特征是：首先晶体硅制造绒面并两面分别镀制i-a-Si，而后两侧分别镀制p-a-Si和n-a-Si；而后利用RPD技术在晶硅异质结顶部和底部分别镀制MGZO薄膜，最后镀制金属电极Ag/Al和Al电极，即构成太阳电池器件。
9.根据权利要求7所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法所得薄膜的应用，其特征是：首先晶体硅制造绒面并两面分别镀制i-a-Si和p-a-Si和n-a-Si；而后电池底部一侧镀制传统TCO薄膜，顶部一侧镀制SnOx/MGZO复合结构薄膜；最后两侧镀制金属电极Ag/Al栅线，即构成太阳电池器件。
10.根据权利要求8或9所述的利用反应等离子沉积技术生长宽光谱MGZO-TCO薄膜的方法所得薄膜的应用，其特征是：所述的太阳电池器件包括晶硅基异质结太阳电池和CIGS太阳电池。
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