太阳能电池用绒面AZO的直接干法制备研究

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摘要

掺铝氧化锌（AZO）薄膜由于具有优异的光电性能，价格低廉、无毒，化学

和热稳定性好，已成为 CuInSe2(CIS)薄膜太阳电池的标准前电极，在非晶硅和微

晶硅薄膜电池中也得到了广泛应用。在用作太阳电池前电极时，AZO 薄膜表面需

要制作绒面增强对入射光的散射。本文研究了 AZO 薄膜制备过程中射频功率、

工作气压、衬底温度对平面薄膜和绒面薄膜光电性能以及表面形貌的影响，制备

了高透光性、低电阻率且具有良好陷光微结构的绒面 AZO 薄膜。

本文中以 K9 玻璃为衬底，采用射频磁控溅射的方法制备 AZO 薄膜，靶材是

Al2O3质量分数为 2%的ZnO 陶瓷靶。分析结果表明，不同工艺参数下制备的 AZO

薄膜都具有 80%以上的可见光平均透过率，电阻率均在 10-3Ω·cm 量级。选用适当

的溅射功率、工作气压和衬底温度可以获得结晶质量好、缺陷少、密度高的 AZO

薄膜。在射频功率为 100w，氩气压强为 0.3Pa，衬底温度为 150℃时制备的厚度

为573nm 的AZO 薄膜在可见光范围平均透过率超过 85% ，电阻率低达

2.27×10-3Ω·cm。

通过对平面薄膜进行 10 分钟的离子束刻蚀后获得了绒面 AZO 薄膜。绒面薄

膜可见光平均透过率比平面薄膜稍有下降，这是由于绒面结构增大了薄膜对入射

光的散射的缘故。刻蚀后的绒面薄膜仍有 80%以上的可见光透过率，完全满足太

阳电池对透明电极透光性能的要求。绒面薄膜的电阻率仍保持在 10-3Ω·cm 量级，

最低为 2.91×10-3Ω·cm，说明绒面薄膜仍具有较好的导电性能。刻蚀后的薄膜表面

布满坑状微结构，微结构分布均匀，横向尺寸约为 0.1~1μm，开口角在 60~150°

之间，具有较好的陷光能力。

本文的研究工作提供了一种新型的透明导电薄膜绒面制备方法，为研制高性

能绒面透明导电薄膜提供了可行的技术方案和可靠的实验数据。

关键词：AZO 薄膜太阳电池绒面磁控溅射离子束刻蚀

ABSTRACT

Aluminum doped zinc oxide(AZO) thin films have been standard front electrodes

for CuInSe2(CIS) thin film solar cells and applied extensively in amorphous and

microcrystalline silicon thin film solar cells since its excellent photoelectric

properties,low cost, non-toxic and high chemical and heat stability. When applied as

front electrodes of solar cells, AZO thin films have to be textured to enhance scattering

of incident light. In this article, the effect of radio frequency (rf) power, argon pressure

and substrate temperature in deposition process on optical and electrical properties and

surface topography of smooth and textured AZO thin films were investigated in detail.

Textured AZO thin films with high light transmittance, low resistivity and efficient

light-trapping structure are prepared.

In this article, AZO thin films are deposited by rf magnetron sputtering using a

zinc oxide target doped with A12O3(2 wt%) on K9 glass substrate. The results indicate

that the average transmittance in visible spectrum of AZO thin films prepared at

different deposition parameters are all above 80%, and resistivity is of the order of

10-3Ω·cm. AZO thin films with good crystallization quality, less defect and high

compactness can be obtained at proper rf power, argon pressure and substrate

temperature. The thin film with lowest resistivity of 2.27×10-3Ω·cm and average

transmittance over 85% in visible spectrum is deposited at rf power of 100w, Argon

pressure of 0.3 Pa, substrate temperature of 150℃and film thickness of 573nm.

Textured AZO thin films are prepared by ion beam etching for 10 minutes to

smooth films. Since the light scattering of textured surface, the average transmittance

in visible spectrum of textured AZO thin films are slightly lower than smooth films.

But the average optical transmittance of all the textured AZO thin films are still higher

than 80% and can fully satisfy the light transmission requirements of transparent

electrode for solar cells. The resistivity of textured films are also of the order of

10-3Ω·cm and can be as low as 2.91×10-3Ω·cm. It shows that textured thin films still

have well electric conductivity. The post-etching surface of thin films are plenty of

craters with lateral diameters between 0.1~1μm, opening angles between 60~150° and

are well-distributed, so textured AZO thin films are effective for light trapping.

The work in this thesis proposes a new-type method to fabricate textured surface

for transparent conductive thin films, and provides practicable technique solution and

trustworthy experiment data for research on excellent textured transparent conductive

thin films.

Key Word: AZO Thin Film, Solar Cell, Textured Surface, Magnetron

Sputtering, Ion Beam Etching

摘要

ABSTRACT

第一章绪论 .............................................................................................................1

§1.1 引言 ..........................................................................................................1

§1.2 本文的研究内容和意义 ..........................................................................1

§1.3 国内外研究的相关技术与成果 ..............................................................2

§1.4 本论文的主要工作 ..................................................................................4

第二章 ZnO 及AZO 薄膜概述 .............................................................................. 5

§2.1 ZnO 和AZO 薄膜的结构特性 ................................................................ 5

§2.2 ZnO 和AZO 薄膜的电学特性 ................................................................ 6

§2.3 ZnO 和AZO 薄膜的光学特性 ................................................................ 9

§2.4 AZO 薄膜的制备方法 ............................................................................10

§2.5 AZO 薄膜的应用 ....................................................................................10

§2.6 本章小结 ................................................................................................11

第三章太阳能电池及陷光模型概述 ...................................................................12

§3.1 太阳能电池的基本原理 ........................................................................12

§3.2 太阳电池中的光吸收 ............................................................................13

§3.2.1 光在半导体中的反射和折射 .....................................................13

§3.2.2 光在半导体中的吸收 .................................................................14

§3.3 太阳电池的陷光结构 ............................................................................15

§3.3.1 晶体硅电池的陷光结构 .............................................................15

§3.3.2 薄膜电池的陷光结构 .................................................................16

§3.3.3 陷光模型及计算 .........................................................................17

§3.4 本章小结 ................................................................................................22

第四章实验方法及仪器设备 ...............................................................................23

§4.1 AZO 薄膜的制备 ....................................................................................23

§4.1.1 AZO 薄膜的制备方法 .................................................................23

§4.1.2 AZO 薄膜沉积系统 .....................................................................24

§4.1.3 实验过程及实验参数 .................................................................25

§4.2 AZO 薄膜绒面的获得 ............................................................................26

§4.2.1 离子束刻蚀原理 ..........................................................................26

§4.2.2 离子束刻蚀系统 ..........................................................................26

§4.2.3 刻蚀实验参数 ..............................................................................27

§4.3 AZO 薄膜的测试 ....................................................................................27

§4.3.1 薄膜光学性能测试 .....................................................................27

§4.3.2 薄膜电学性能测试 .....................................................................28

§4.3.3 薄膜厚度测试 .............................................................................28

§4.3.4 薄膜表面形貌测试 .....................................................................29

§4.4 本章小结 .................................................................................................30

第五章 AZO 薄膜的测试与分析 ..........................................................................31

§5.1 膜层厚度的影响 ....................................................................................31

§5.1.1 膜层厚度对薄膜光学性能的影响 .............................................31

§5.1.2 膜层厚度对薄膜电学性能的影响 .............................................32

§5.2 溅射功率的影响 ....................................................................................33

§5.2.1 溅射功率对薄膜沉积速率的影响 .............................................33

§5.2.2 溅射功率对薄膜光学性能的影响 .............................................33

§5.2.3 溅射功率对薄膜电学性能的影响 .............................................34

§5.2.4 溅射功率对薄膜表面形貌的影响 .............................................35

§5.3 工作气压的影响 ....................................................................................36

§5.3.1 工作气压对薄膜沉积速率的影响 .............................................36

§5.3.2 工作气压对薄膜光学性能的影响 .............................................36

§5.3.3 工作气压对薄膜电学性能的影响 .............................................37

§5.3.4 工作气压对薄膜表面形貌的影响 .............................................38

§5.4 衬底温度的影响 ....................................................................................39

§5.4.1 衬底温度对薄膜沉积速率的影响 .............................................39

§5.4.2 衬底温度对薄膜光学性能的影响 .............................................39

§5.4.3 衬底温度对薄膜电学性能的影响 .............................................40

§5.4.4 衬底温度对薄膜表面形貌的影响 .............................................41

§5.5 本章小结 ................................................................................................42

第六章绒面 AZO 薄膜的测试与分析 ................................................................ 43

§6.1 薄膜制备工艺参数对刻蚀速率的影响 .................................................43

§6.1.1 射频功率对刻蚀速率的影响 .....................................................43

§6.1.2 工作气压对刻蚀速率的影响 .....................................................44

§6.1.3 衬底温度对刻蚀速率的影响 .....................................................44

§6.2 绒面薄膜的光学性能 ............................................................................45

§6.2.1 刻蚀后薄膜的透光性能 .............................................................45

§6.2.2 绒面薄膜与平面薄膜平均透过率的比较 .................................46

§6.3 绒面薄膜的电学性能 ............................................................................48

§6.3.1 射频功率对绒面薄膜电阻率的影响 .........................................48

§6.3.2 工作气压对绒面薄膜电阻率的影响 .........................................48

§6.3.3 衬底温度对绒面薄膜电阻率的影响 .........................................49

§6.4 绒面薄膜的表面形貌 ............................................................................50

§6.4.1 射频功率对绒面薄膜表面形貌的影响 .....................................50

§6.4.2 工作气压对绒面薄膜表面形貌的影响 .....................................51

§6.4.3 衬底温度对绒面表面薄膜形貌的影响 .....................................52

§6.5 本章小结 ................................................................................................53

第七章总结与展望 ...............................................................................................54

§7.1 总结 ........................................................................................................54

§7.2 后续研究与展望 ....................................................................................55

参考文献 .................................................................................................................56

在读期间公开发表的论文和承担科研项目及取得成果 .....................................60

致谢 .......................................................................................................................61

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摘要：

摘要掺铝氧化锌（AZO）薄膜由于具有优异的光电性能，价格低廉、无毒，化学和热稳定性好，已成为CuInSe2(CIS)薄膜太阳电池的标准前电极，在非晶硅和微晶硅薄膜电池中也得到了广泛应用。在用作太阳电池前电极时，AZO薄膜表面需要制作绒面增强对入射光的散射。本文研究了AZO薄膜制备过程中射频功率、工作气压、衬底温度对平面薄膜和绒面薄膜光电性能以及表面形貌的影响，制备了高透光性、低电阻率且具有良好陷光微结构的绒面AZO薄膜。本文中以K9玻璃为衬底，采用射频磁控溅射的方法制备AZO薄膜，靶材是Al2O3质量分数为2%的ZnO陶瓷靶。分析结果表明，不同工艺参数下制备的AZO薄膜都具有80%以上的可见光...

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