四乙基氢氧化铵界面修饰制备高效甲脒溴化铅钙钛矿太阳能电池

doi:10.6023/A25100347

化学学报 ›› 2026, Vol. 84 ›› Issue (2): 231-239.DOI: 10.6023/A25100347 上一篇下一篇

研究论文

四乙基氢氧化铵界面修饰制备高效甲脒溴化铅钙钛矿太阳能电池

汪佳艳^a, 郭焕焕^b^,^*(), 殷逍遥^a, 张昀照^a, 王威^a, 赵晨瑞^a, 陈洁^a, 文洁^a, 孙伟海^a^,^*()

^a 华侨大学材料科学与工程学院物理化学研究所环境友好功能材料教育部工程研究中心福建省光电功能材料重点实验室厦门 361021
^b 邢台学院化学工程与生物技术学院河北邢台 054001

投稿日期:2025-10-19 发布日期:2026-01-29
基金资助:
国家自然科学基金(61804058); 华侨大学中青年教师科研提升资助计划(ZQN-706); 河北省教育厅科学研究项目(BJK2022068); 河北省引进留学人员资助项目(C20220306); 邢台学院教育教学研究与实践项目(JGZ24002)

Preparation of High-Efficiency Formamidinium Lead Bromide (FAPbBr₃) Perovskite Solar Cells via Tetraethylammonium Hydroxide (TEAOH) Interface Modification

Jiayan Wang^a, Huanhuan Guo^b^,^*(), Xiaoyao Yin^a, Yunzhao Zhang^a, Wei Wang^a, Chenrui Zhao^a, Jie Chen^a, Jie Wen^a, Weihai Sun^a^,^*()

^a Institute of Physical Chemistry, College of Materials Science and Engineering, Huaqiao University; Engineering Research Center of Environment-Friendly Functional Materials, Ministry of Education; Fujian Provincial Key Laboratory of Optoelectronic Functional Materials, Xiamen 361021, China
^b College of Chemical Engineering and Biotechnology, Xingtai University, Xingtai 054001, Hebei, China

Received:2025-10-19 Published:2026-01-29
Contact: *E-mail: claireguo1124@hotmail.com;sunweihai@hqu.edu.cn
Supported by:
National Natural Science Foundation of China(61804058); Young and Middle-aged Teachers' Scientific Research Promotion Program of Huaqiao University(ZQN-706); Scientific Research Project of the Education Department of Hebei Province(BJK2022068); Overseas Returnees Support Program of Hebei Province(C20220306); Education and Teaching Research and Practice Project of Xingtai University(JGZ24002)

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1. Supporting Information-A25100347.pdf(294KB)

摘要/Abstract

近些年来, 甲脒溴化铅(FAPbBr₃)钙钛矿太阳能电池凭借着较宽的带隙、出色的环境稳定性以及较高的开路电压, 在叠层电池、半透明器件以及光催化等多个领域受到了广泛的关注. 本研究采用两步溶液旋涂法制备FAPbBr₃钙钛矿薄膜, 在TiO₂电子传输层上引入了四乙基氢氧化铵(TEAOH)作为界面修饰剂. 通过系统的表征分析发现, TEAOH溶液浓度为4 mg•mL⁻¹时达到最佳光伏性能, 展现出显著的形貌改善, 直接导致了薄膜质量的提升, 缺陷态密度更低, 从而抑制了载流子的复合. 最终制备最优器件, 开路电压(open-circuit voltage, V_OC)为1.63 V, 短路电流密度(short-circuit current density, J_SC)为7.99 mA•cm⁻², 填充因子(fill factor, FF)为83.74%, 光电转换效率(photoelectric conversion efficiency, PCE)达10.91%, 并且目前该值是在无空穴传输层(hole transport layer, HTL) FAPbBr₃器件里报道的最高值.

关键词: FAPbBr₃钙钛矿太阳能电池, TiO₂/FAPbBr₃层, 四乙基氢氧化铵, 两步旋涂, 界面修饰

Formamidinium lead bromide (FAPbBr₃) perovskite solar cells (PSCs) have attracted increasing attention for applications in tandem photovoltaics, semi-transparent devices, and photocatalysis owing to their wide bandgap, excellent thermal stability, and high open-circuit voltage. Compared with iodide-based perovskites, FAPbBr₃ exhibits superior resistance to moisture, heat, and phase instability. However, its relatively wide bandgap limits the short-circuit current density in single-junction devices, and severe interfacial defect-induced nonradiative recombination at the electron transport layer (ETL)/perovskite interface further constrains device performance, especially in hole-transport-layer-free (HTL-free) architectures. In this work, high-quality FAPbBr₃ perovskite films were fabricated via a two-step solution spin-coating method, in which PbBr₂ films were first deposited followed by the spin-coating of a formamidinium bromide (FABr) methanol solution. To regulate interfacial charge transport and suppress defect-assisted recombination, tetraethylammonium hydroxide (TEAOH) was introduced as an interfacial modifier at the TiO₂/FAPbBr₃ interface. By systematically tuning the concentration of the TEAOH aqueous solution, the influence of interfacial modification on perovskite crystallization, defect passivation, and carrier dynamics was comprehensively investigated. Morphological characterization by scanning electron microscopy revealed that an optimal TEAOH concentration of 4 mg•mL⁻¹ significantly improved the film quality, featuring enlarged grain size, reduced grain boundary density, and a more compact and uniform morphology. X-ray diffraction analysis confirmed enhanced crystallinity and improved phase purity of the FAPbBr₃ films after TEAOH modification. Meanwhile, ultraviolet-visible absorption spectra demonstrated strengthened light-harvesting capability, which can be attributed to the improved microstructure and reduced optical scattering losses. Electrical and spectroscopic analyses, including steady-state and time-resolved photoluminescence, space-charge-limited current measurements, electrochemical impedance spectroscopy, and transient optoelectronic characterization, consistently revealed that TEAOH modification effectively reduced interfacial defect density, suppressed nonradiative recombination, and promoted faster electron extraction at the TiO₂/FAPbBr₃ interface. As a result, the optimized HTL-free FAPbBr₃ PSC delivered a high open-circuit voltage of 1.63 V, a short-circuit current density of 7.99 mA•cm⁻², and a fill factor of 83.74%, achieving a power conversion efficiency of 10.91%, which represents the highest reported efficiency for HTL-free FAPbBr₃-based PSCs to date. In addition, the modified devices exhibited stable current output under continuous illumination. This study demonstrates that TEAOH interfacial engineering is a simple yet highly effective strategy to simultaneously improve crystallization quality, interfacial charge transport, and photovoltaic performance in wide-bandgap perovskite solar cells, offering valuable insights for the development of efficient and stable perovskite optoelectronic devices.

Key words: FAPbBr₃ perovskite solar cells, TiO₂/FAPbBr₃ interface, tetraethylammonium hydroxide, two-step spin-coating, interfacial modification

引用此文

汪佳艳, 郭焕焕, 殷逍遥, 张昀照, 王威, 赵晨瑞, 陈洁, 文洁, 孙伟海. 四乙基氢氧化铵界面修饰制备高效甲脒溴化铅钙钛矿太阳能电池[J]. 化学学报, 2026, 84(2): 231-239.

Jiayan Wang, Huanhuan Guo, Xiaoyao Yin, Yunzhao Zhang, Wei Wang, Chenrui Zhao, Jie Chen, Jie Wen, Weihai Sun. Preparation of High-Efficiency Formamidinium Lead Bromide (FAPbBr₃) Perovskite Solar Cells via Tetraethylammonium Hydroxide (TEAOH) Interface Modification[J]. Acta Chimica Sinica, 2026, 84(2): 231-239.

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图/表 8

图1. TEAOH界面修饰层和FAPbBr3薄膜制备流程图

Figure 1. Schematic illustration of the TEAOH interface modification layer and the fabrication process of the FAPbBr3 film

图2. (a)空白, (b) 4 mg•mL−1 TEAOH修饰的TiO2薄膜平面SEM图; (c)空白组, (d) 3 mg•mL−1, (e) 4 mg•mL−1, (f) 5 mg•mL−1 TEAOH修饰后的FAPbBr3钙钛矿薄膜的平面SEM图

Figure 2. Plan-view SEM images of (a) unmodified TiO2 film; (b) TiO2 film modified with an optimal concentration of TEAOH; (c) pristine FAPbBr3 perovskite film; and (d~f) FAPbBr3 perovskite films modified with TEAOH at concentrations of 3, 4, and 5 mg•mL−1, respectively

图3. (a)空白组和不同浓度TEAOH修饰的PSCs器件的XRD谱图; (b)空白组和TEAOH修饰的PSCs器件薄膜的UV-Vis吸收光谱; (c)空白组和不同质量浓度TEAOH溶液界面修饰FAPbBr3 PSCs的J-V曲线; (d)空白组和TEAOH修饰的PSCs器件的稳态输出曲线

Figure 3. (a) XRD patterns of PSC devices without modification (pristine) and with different concentrations of TEAOH treatment; (b) UV-Vis absorption spectra of perovskite films of pristine and TEAOH-modified PSC devices; (c) J-V curves of FAPbBr3 PSCs with interfacial modification using TEAOH solutions of different concentrations and the pristine group; (d) steady-state output curves of PSCs from the pristine group and those modified with TEAOH

Sample	V_OC/V	J_SC/(mA•cm⁻²)	FF/%	PCE/%
Pristine	1.49	7.33	77.84	8.50
TEAOH-5	1.57	7.73	81.98	9.95
TEAOH-4	1.63	7.99	83.74	10.91
TEAOH-3	1.52	7.49	78.12	8.89

表1. 不同质量浓度TEAOH界面修饰的FAPbBr3 PSCs的光伏参数

Table 1. Photovoltaic parameters of FAPbBr3 PSCs with interfacial modification using TEAOH at different concentrations

图4. 空白组和4 mg•mL−1 TEAOH修饰的PSCs器件薄膜的(a) PL谱图, (b) TRPL谱图, (c) SCLC曲线图和(d)暗态EIS图

Figure 4. The (a) PL spectrum, (b) TRPL spectrum, (c) SCLC curve and (d) dark-state EIS diagram of the pristine group and 4 mg•mL−1 TEAOH-modified PSC device films

Sample	τ_ave/ns	A₁/%	τ₁/ns	A₂/%	τ₂/ns
Pristine	35.524	77.58	43.233	22.42	8.843
TEAOH	21.328	56.35	32.817	43.65	6.498

表2. 空白组和TEAOH修饰的PSCs器件薄膜的TRPL曲线参数

Table 2. TRPL fitting parameters of the PSCs films for the pristine group and the TEAOH-modified group

图5. 空白组和4 mg•mL−1 TEAOH修饰的PSCs器件的(a) TPC曲线, (b) TPV曲线, (c) JSC与光强的依赖性和(d) C-V曲线

Figure 5. The (a) TPC curve, (b) TPV curve, (c) dependence of JSC on light intensity, and (d) C-V curve of the pristine group and 4 mg•mL−1 TEAOH-modified PSC devices

图6. 30组空白组和TEAOH修饰的PSCs器件的(a) VOC箱线图, (b) FF箱线图, (c) JSC箱线图, (d) PCE箱线图; 空白组和TEAOH修饰的PSCs器件的30 d稳定性测试: (e) VOC稳定性, (f) FF稳定性, (g) JSC稳定性, (h) PCE稳定性

Figure 6. The (a) VOC box plot, (b) FF box plot, (c) JSC box plot, (d) PCE box plot of the 30 sets of pristine group and TEAOH-modified PSC devices; The (e) VOC stability, (f) FF stability, (g) JSC stability, (h) PCE stability from the 30-day stability test of the pristine group and TEAOH-modified PSC devices

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四乙基氢氧化铵界面修饰制备高效甲脒溴化铅钙钛矿太阳能电池

Preparation of High-Efficiency Formamidinium Lead Bromide (FAPbBr₃) Perovskite Solar Cells via Tetraethylammonium Hydroxide (TEAOH) Interface Modification

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四乙基氢氧化铵界面修饰制备高效甲脒溴化铅钙钛矿太阳能电池

Preparation of High-Efficiency Formamidinium Lead Bromide (FAPbBr3) Perovskite Solar Cells via Tetraethylammonium Hydroxide (TEAOH) Interface Modification

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Preparation of High-Efficiency Formamidinium Lead Bromide (FAPbBr₃) Perovskite Solar Cells via Tetraethylammonium Hydroxide (TEAOH) Interface Modification