硅酸盐学报

基于碘化胍体相掺杂的碳基钙钛矿太阳能电池性能调控

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朱粮苹 ¹ , 赵文燕 ¹^,² , 付少剑 ³ , 田传进 ¹^,² , 张彩龙 ¹ , 韩曦曦 ¹ , 刘钰旻 ¹ , 汪长安 ⁴ , 谢志鹏 ⁴

硅酸盐学报 | 研究论文 2026,54(3): 1072-1082

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硅酸盐学报 |研究论文 2026 , 54 (3) : 1072 -1082

基于碘化胍体相掺杂的碳基钙钛矿太阳能电池性能调控

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朱粮苹¹, 赵文燕¹^,², 付少剑³, 田传进¹^,², 张彩龙¹, 韩曦曦¹, 刘钰旻¹, 汪长安⁴, 谢志鹏⁴

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西省先进陶瓷材料重点实验室，江西景德镇 333001

^2．景德镇陶瓷大学，国家日用及建筑陶瓷工程技术研究中心，江西景德镇 333001

^3．淮安捷泰新能源科技有限公司，江苏淮安 223001

^4．清华大学材料学院，新型陶瓷国家重点实验室，北京 100084

通讯作者:

赵文燕（1981—），女，博士，教授

汪长安（1969—），男，博士，教授。

作者简介:

朱粮苹（1999—），男，硕士研究生。

Guanidine Iodide Bulk Doping Engineering for Carbon-Based Perovskite Photovoltaics with Hole Transport Layer-Free Architecture

Liangping ZHU¹, Wenyan ZHAO¹^,², Shaojian FU³, Chuanjin TIAN¹^,², Cailong ZHANG¹, Xixi HAN¹, Yumin LIU¹, Changan WANG⁴, Zhipeng XIE⁴

Affiliations

^1.Jiangxi Key Laboratory of Advanced Ceramic Materials, School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333001, Jiangxi, China

^2.National Engineering Research Center for Domestic & Building Ceramics, Jingdezhen Ceramic University, Jingdezhen 333001, Jiangxi, China

^3.Huai-an Jietai New Energy Technology Co., Ltd, Huai-an 223001, Jiangsu, China

^4.State Key Laboratory of New Ceramics Materials, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China

Corresponding Author:

ZHAO Wenyan (1981-), female, Ph.D., Professor. E-mail: zhaowenyan223@126.com

WANG Chang-an (1969-), male, Ph.D., Professor. E-mail: wangca@mail.tsinghua.edu.cn.

ZHU Liangping (1999-), male, Master candidate. E-mail: 15279993059@163.com

出版时间: 2026-03-20 doi: 10.14062/j.issn.0454-5648.20250255

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摘要

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无空穴传输层碳基钙钛矿太阳能电池（C-PSC）因其制造成本低、稳定性好和制造工艺简单而成为商用太阳能电池的有力竞争者。然而，基于一步溶液法制备的钙钛矿薄膜依然存在由薄膜质量引起的效率和稳定性问题，这将会阻碍其商业化进程。为了解决这些问题，本工作引入胍盐（GAI）以调节钙钛矿结晶过程，改善薄膜质量。GAI能够少量掺入钙钛矿晶格，且通过形成强氢键网络（N—H...I）抑制缺陷生成，稳定晶格结构。此外，GAI被证明能够促进薄膜生长、减少体相缺陷以及抑制载流子的非辐射复合。结果表明，基于GAI掺杂的器件实现了17.33%的功率转换效率，而对照组仅为15.7%。同时，器件的稳定性也得到了较大的提升，未封装的器件在空气中存放600h后，掺入GAI的器件保持初始效率的95%，而对照组不足90%。这为开发高效、稳定的碳基钙钛矿太阳能电池提供了新的思路。

关键词

碳基钙钛矿太阳能电池 / 无空穴传输层 / 增材工程 / 碘化胍 / 氢键网络

Abstract

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Introduction

Perovskite solar cells (PSCs) as a representative of third-generation photovoltaic technology have achieved remarkable progress. Their power conversion efficiency (PCE) is significantly enhanced from the initial 3.8% reported in 2009 to the 27% in 2025. Compared to conventional designs that employ expensive hole transport layer (HTL) materials and noble metal electrodes, carbon is considered as an ideal substitute for noble metal electrodes due to its unique structural diversity, chemical stability, and rich surface chemistry. Also, a similarity between the Fermi level of carbon materials and that of metals gives carbon electrodes an advantageous edge in practical applications. HTL-Free carbon-based perovskite solar cells (C-PSCs) typically adopt an HTL-free structure, which simplifies the fabrication process and positions them as promising candidates for single-junction solar cells. However, a direct contact between carbon electrodes and perovskite surfaces inevitably exacerbates a non-radiative recombination that may occur during thin-film preparation. This study was thus to introduce guanidinium iodide (GAI) into perovskite films based on the FAMACsPbI₃ system. GAI could effectively passivate iodine defects and promotes crystal growth and enhance crystal stability through a robust hydrogen-bond network, thereby significantly improving the efficiency and stability of C-PSCs.

Methods

Perovskite precursor solutions were prepared via dissolving lead iodide (PbI₂), formamidinium iodide (FAI), methylammonium chloride (MACl), cesium iodide (CsI), and methylammonium iodide (MAI) in a mixed solvent of N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), with different concentrations of guanidinium iodide (GAI) (i.e., 0, 1, 2 mg·mL^-1 and 3 mg·mL^-1) as dopants. The perovskite layer was then deposited on a substrate pre-coated with a TiO₂ layer by a one-step spin-coating method, followed by annealing on a hotplate at 150 ℃ for 13 min. A conductive carbon paste was uniformly blade-coated onto the surface of the perovskite active layer and annealed at 100 ℃ for 10 min to complete the fabrication of the perovskite solar cell.

The crystal phase and morphology of the films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The surface composition, chemical states, and elemental information of the perovskite films were determined by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The optical absorption properties and energy band variations were analyzed by ultraviolet-visible (UV-vis) spectroscopy and steady-state/time-resolved photoluminescence (PL) measurements. The carrier separation/transport dynamics and defect state density in the devices were evaluated by electrochemical impedance spectroscopy (EIS), Mott-Schottky (M-S) analysis, space-charge-limited current (SCLC) measurements, and dark current-voltage (I-V) curves. The performance enhancement of GAI-doped perovskite devices was further investigated via measuring current density-voltage (J-V) characteristics under simulated sunlight.

Results and discussion

The XRD patterns of samples doped with varying concentrations of GAI (i.e., 0, 1, 2 mg·mL^-1 and 3 mg·mL^-1) reveal that the perovskite lattice expands with increasing GAI concentration, as evidenced by a gradual shift of diffraction peaks toward lower angles. At a doping concentration of 2 mg·mL^-1, the perovskite exhibits an optimal crystallinity. The AFM and SEM characterization further demonstrates a reduced surface roughness, an enlarged grain size, and an improved film smoothness. The PL measurements show a significantly enhanced peak intensity at the GAI doping level of 2 mg·mL^-1, corroborating a positive role of GAI in promoting perovskite crystallization. The XPS and FTIR analysis elucidates the impact of GAI doping on the internal lattice structure, confirming the presence of hydrogen bonding (N—H...I) and clarifying the mechanistic role of GAI during perovskite crystallization. The effect of GAI doping on the carrier separation and transport is systematically investigated through EIS, Mott-Schottky (MS), SCLC, and dark current measurements. The results indicate that GAI incorporation increases a recombination resistance, suppresses a non-radiative recombination, facilitates a photogenerated carrier separation, and reduces a defect state density from 1.58×10¹⁶ cm^-3 to 1.17×10¹⁶ cm^-3. Consequently, the GAI-doped device achieves a champion power conversion efficiency (PCE) of 17.33%, outperforming the control device (15.7%). In addition, the results of stability tests demonstrate a remarkable improvement (i.e., unencapsulated devices retain approximately 95% of their initial efficiency after 600 h of ambient storage, whereas the control group degrades to below 90%).

Conclusions

This study proposed a low-concentration GAI-doped bulk passivation technique for perovskite films. The research demonstrated that moderate GAI doping could promote a perovskite crystal growth and significantly mitigate both bulk and interfacial defects. Consequently, GAI-doped perovskite films could effectively suppress a non-radiative recombination, enhance carrier transport, and substantially improve the efficiency and stability of HTL-free carbon-based perovskite solar cells (C-PSCs). A high power conversion efficiency of 17.33% was achieved through this strategy. The unencapsulated devices retained approximately 95% of their initial efficiency after 600 hours of exposure to ambient air, exceeding the performance of the control group. These findings could provide a novel research direction for developing highly efficient and stable C-PSCs.

Key words

carbon-based perovskite solar cells / hole transport layer-free / additive engineering / guanidine iodide / hydrogen bond network

引用本文

朱粮苹, 赵文燕, 付少剑, 田传进, 张彩龙, 韩曦曦, 刘钰旻, 汪长安, 谢志鹏. 基于碘化胍体相掺杂的碳基钙钛矿太阳能电池性能调控. 硅酸盐学报, 2026 , 54 (3) : 1072 -1082 . DOI: 10.14062/j.issn.0454-5648.20250255

Liangping ZHU, Wenyan ZHAO, Shaojian FU, Chuanjin TIAN, Cailong ZHANG, Xixi HAN, Yumin LIU, Changan WANG, Zhipeng XIE. Guanidine Iodide Bulk Doping Engineering for Carbon-Based Perovskite Photovoltaics with Hole Transport Layer-Free Architecture[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (3) : 1072 -1082 . DOI: 10.14062/j.issn.0454-5648.20250255

基金

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国家自然科学基金(52162028)
江西省科技厅自然科学基金(20232ACB204011; 20224BAB204001)
江西省教育厅自然科学基金(GJJ2201001)
景德镇市科技局项目(2023GY001-16; 20224SF005-08; 2023ZDGG001)
国家日用及建筑陶瓷工程技术研究中心开放课题基金(GCZX2301)
新型陶瓷材料国家重点实验室开放课题(KF202309; KF202414)
景德镇陶瓷大学研究生创新基金(JYC202313)

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排序方式：

2026年第54卷第3期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250255

接收时间：2025-04-08
首发时间：2026-10-27
出版时间：2026-03-20

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出版历史

收稿日期：2025-04-08
修回日期：2025-05-16

基金

国家自然科学基金(52162028)

江西省科技厅自然科学基金(20232ACB204011; 20224BAB204001)

江西省教育厅自然科学基金(GJJ2201001)

景德镇市科技局项目(2023GY001-16; 20224SF005-08; 2023ZDGG001)

国家日用及建筑陶瓷工程技术研究中心开放课题基金(GCZX2301)

新型陶瓷材料国家重点实验室开放课题(KF202309; KF202414)

景德镇陶瓷大学研究生创新基金(JYC202313)

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西省先进陶瓷材料重点实验室，江西景德镇 333001

^2．景德镇陶瓷大学，国家日用及建筑陶瓷工程技术研究中心，江西景德镇 333001

^3．淮安捷泰新能源科技有限公司，江苏淮安 223001

^4．清华大学材料学院，新型陶瓷国家重点实验室，北京 100084

通讯作者:

赵文燕（1981—），女，博士，教授

汪长安（1969—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250255

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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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