硅酸盐学报

氧化锌/锡酸锌/二氧化锡双异质结纳米阵列的构建及其光电性能

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周龙杰 ¹ , 王航 ¹ , 刘硕 ¹ , 李丽华 ¹^,² , 黄金亮 ¹^,²

硅酸盐学报 | 研究论文 2024,52(7): 2308-2315

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硅酸盐学报 |研究论文 2024 , 52 (7) : 2308 -2315

氧化锌/锡酸锌/二氧化锡双异质结纳米阵列的构建及其光电性能

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周龙杰¹, 王航¹, 刘硕¹, 李丽华¹^,², 黄金亮¹^,²

作者信息

^1．河南科技大学材料科学与工程学院，河南洛阳 471023

^2．有色金属新材料与先进加工技术省部共建协同创新中心，河南洛阳 471023

通讯作者:

黄金亮（1963—），男，博士，教授。

作者简介:

周龙杰（1998—），男，硕士研究生。

Construction and Photoelectrochemical Performance of Zinc Oxide/Zinc Stannate/Tin Dioxide Double Heterojunction Nanoarray

Longjie ZHOU¹, Hang WANG¹, Shuo LIU¹, Lihua LI¹^,², Jinliang HUANG¹^,²

Affiliations

^1.School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, Henan, China

^2.Provincial and Ministerial Co-construction of Collaborative Innovation Center for Non-ferrous Metal New Materials and Advanced Processing Technology, Luoyang 471023, Henan, China

Corresponding Author:

HUANG Jinliang (1963-), male, Ph.D., Professor. E-mail: huangjl@haust.edu.cn

ZHOU Longjie (1998-), male, Master candidate. E-mail: zhoulj@stu.haust.edu.cn

出版时间: 2024-07-20 doi: 10.14062/j.issn.0454-5648.20230487

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摘要

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高性能的电子传输传输层对提升钙钛矿太阳能电池的光电转化效率具有至关重要的作用。基于表面修饰的方法，采用旋涂法在ZnO纳米阵列上制备Zn₂SnO₄钝化层，再通过水热法原位自生长SnO₂构建出ZnO/Zn₂SnO₄/SnO₂双异质结纳米阵列。利用X射线衍射、场发射扫描电镜、透射电子显微镜对异质结的物相、形貌进行了观察和分析，并通过电化学工作站对其光电性能进行了测试。结果表明：Zn₂SnO₄和SnO₂都成功负载在ZnO上，三者之间交错的能带结构所形成的双Ⅱ型异质结进一步提高了光生电子-空穴对分离效率，使得ZnO/Zn₂SnO₄/SnO₂双异质结纳米阵列的电流密度以及光电流较ZnO得到了明显的改善，同时电荷转移电阻从22 403 Ω降低至3 131 Ω，载流子浓度从1.22×10¹⁹ cm^-3降低至1.18×10¹⁸ cm^-3，光电性能提升明显。

关键词

氧化锌/锡酸锌/二氧化锡 / 双异质结 / 载流子分离 / 光电性能

Abstract

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Introduction

As an important part of perovskite solar cells, the electron transport layer plays a role in transporting electrons and blocking holes, having an impact on the performance of perovskite cells. ZnO is a promising electron transport layer (ETL) material because of its high electron mobility, easy synthesis, low-temperature preparation and low cost. However, the chemical properties of ZnO are unstable, and the surface defects are easy to form recombination centers, leading to the decline of electron extraction and transfer efficiency, and surface residual groups destroy the perovskite structure and reduce the stability of perovskite materials, resulting in the deterioration of device performance. Therefore, selecting a suitable modification layer to improve the stability of ZnO plays an important role in improving the performance of ZnO and perovskite batteries.

Methods

ZnO/Zn₂SnO₄ NAs was prepared on ZnO NAs surface by a spin-coating method to passivate ZnO surface defects and residual groups. ZnO/Zn₂SnO₄/SnO₂ NAs was formed via in-situ growth of a layer of SnO₂ by a hydrothermal method to improve the stability of ZnO.

The phase and morphology of the heterojunction were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The photoelectric performance was measured in electrochemical workstation, in which the photoelectric response ability of the nanoarray was characterized by linear sweep voltammetry. The separation performance of photogenerated electrons and holes in nanoarrays was analyzed via the change of photocurrent. The charge transfer resistance was determined by electrochemical impedance spectroscopy. The conductive type of the semiconductor was determined via the Mott-Schottky test, and the passivation effect of Zn₂SnO₄ and SnO₂ on the ZnO surface defects was reflected by the carrier concentration.

Results and discussion

The results by XRD, SEM and TEM show that Zn₂SnO₄ and SnO₂ are coated on ZnO nanoarrays. Zn₂SnO₄ as a protective layer has a superior chemical stability in alkaline environment to prevent direct contact between ZnO and OH^- produced by urea hydrolysis, avoiding the corrosion of ZnO. This is beneficial to improving the stability and photoelectric properties of ZnO.

The linear scanning voltammetry curves of ZnO, ZnO/SnO₂, ZnO/Zn₂SnO₄ and ZnO/Zn₂SnO₄/SnO₂ NAs at 0-0.6 V vs. RHE under light conditions indicate that ZnO/Zn₂SnO₄/SnO₂ NAs have the maximum photocurrent density. These results demonstrate that the photoelectric response of nanoarrays can be improved via the modification of Zn₂SnO₄. ZnO/Zn₂SnO₄ and ZnO/Zn₂SnO₄/SnO₂ NAs modified with Zn₂SnO₄ exhibit a higher photocurrent. The ZnO/Zn₂SnO₄/SnO₂ NAs photocurrent (i.e., 140 μA·cm^-2) is 1.75 times greater than that of ZnO NAs photocurrent (i.e., 80 μA·cm^-2). This indicates that the addition of Zn₂SnO₄ and the construction of double heterojunction have a positive effect on reducing the electron-hole pair recombination phenomenon and improving the photoelectric performance of nanoarray. The charge transfer resistances of ZnO, ZnO/SnO₂, ZnO/Zn₂SnO₄, ZnO/Zn₂SnO₄/SnO₂ NAs measured by electrochemical impedance spectroscopy are 22 403 Ω, 16 854 Ω, 7 018 Ω and 3 131 Ω, respectively. The Zn₂SnO₄ modified layer reduces a charge transfer resistance via passivating the ZnO surface defects and reducing the scattering effect of the defects on the carriers. The ZnO/Zn₂SnO₄/SnO₂ co-constructed heterojunction structure promotes the separation of electron-hole pairs and electron transport at the interface, further reducing the resistance of photogenerated electrons to transfer at the interface. In the Mott-Schottky test, the carrier concentrations of ZnO, ZnO/Zn₂SnO₄, ZnO/SnO₂, ZnO/Zn₂SnO₄/SnO₂ NAs are 1.22×10¹⁹, 2.34×10¹⁸, 2.41×10¹⁸ and 1.18×10¹⁸ cm^-3, respectively. ZnO defects are passivated by Zn₂SnO₄ modification, and the carrier recombination center is reduced. The carrier concentration of ZnO/Zn₂SnO₄/SnO₂ NAs is lower than that of ZnO NAs. ZnO, Zn₂SnO₄ and SnO₂ form a double type II heterojunction with interlaced arrangement of energy level, which drives a transfer of photogenerated electrons from high energy level to low energy level, so that the photogenerated electron-hole pair can be effectively separated at the interface, thus effectively reducing the electron and hole recombination. It also reduces a charge transfer resistance and promotes a photogenerated electron transfer from SnO₂ to ZnO. The photoelectric properties of ZnO/Zn₂SnO₄/SnO₂ (i.e., current density, photocurrent and carrier concentration) are improved.

Conclusion

ZnO NAs surface was coated with Zn₂SnO₄ nanocrystals by a spin-coating method. Zn₂SnO₄ reduced the recombination of photo-generated charge carriers at the interface via passivating the defects and residual groups on ZnO NAs surface. Based on ZnO surface defects passivated by Zn₂SnO₄, a more stable and high-density SnO₂ nanoparticle coating layer was in-situ grown on ZnO/Zn₂SnO₄ NAs by a hydrothermal method, and the double heterojunction was formed with ZnO and Zn₂SnO₄. The alternating energy level arrangement could improve the separation efficiency of photogenerated charge carriers. The constructed ZnO/Zn₂SnO₄/SnO₂ NAs had higher current density, photocurrent, lower charge transfer resistance and carrier concentration, which could be used as an electron transport layer in perovskite solar cells.

Key words

zinc oxide/zinc stannate/tin dioxide / dual-heterojunction / carrier separation / photoelectric performance

引用本文

周龙杰, 王航, 刘硕, 李丽华, 黄金亮. 氧化锌/锡酸锌/二氧化锡双异质结纳米阵列的构建及其光电性能. 硅酸盐学报, 2024 , 52 (7) : 2308 -2315 . DOI: 10.14062/j.issn.0454-5648.20230487

Longjie ZHOU, Hang WANG, Shuo LIU, Lihua LI, Jinliang HUANG. Construction and Photoelectrochemical Performance of Zinc Oxide/Zinc Stannate/Tin Dioxide Double Heterojunction Nanoarray[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (7) : 2308 -2315 . DOI: 10.14062/j.issn.0454-5648.20230487

基金

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高端外国专家项目(GDW2017410125)

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2024年第52卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230487

接收时间：2023-07-11
首发时间：2026-10-22
出版时间：2024-07-20

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收稿日期：2023-07-11
修回日期：2023-09-22

基金

高端外国专家项目(GDW2017410125)

作者信息

^1．河南科技大学材料科学与工程学院，河南洛阳 471023

^2．有色金属新材料与先进加工技术省部共建协同创新中心，河南洛阳 471023

通讯作者:

黄金亮（1963—），男，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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