High-efficiency colorful perovskite solar cells using TiO2 nanobowl arrays as a structured electron transport layer

More info
  • ReceivedMay 31, 2019
  • AcceptedJun 3, 2019
  • PublishedJul 2, 2019


The rapid development of perovskite solar cells (PSCs) has stimulated great interest in the fabrication of colorful PSCs to meet the needs of aesthetic purposes in varied applications including building integrated photovoltaics and wearable electronics. However, it remains challenging to prepare high-efficiency PSCs with attractive colors using perovskites with broad optical absorption and large absorption coefficients. Here we show that high-efficiency PSCs exhibiting distinct structural colors can be readily fabricated by employing TiO2 nanobowl (NB) arrays as a nanostructured electron transport layer to integrate with a thin overlayer of perovskite on the NB arrays. A new crystalline precursor film based on lead acetate was prepared through a Lewis acid-base adduct approach, which allowed for the formation of a uniform overlayer of high-quality CH3NH3PbI3 crystals on the inner walls of the NBs. The PSCs fabricated using the TiO2 NB arrays showed angle-dependent vivid colors under light illumination. The resultant colorful PSCs exhibited a remarkable photovoltaic performance with a champion efficiency up to 16.94% and an average efficiency of 15.47%, which are record-breaking among the reported colorful PSCs.

Funded by

the National Natural Science Foundation of China(21673007)


This work was supported by the National Natural Science Foundation of China (21673007). The authors were grateful to Xue Zhou and Prof. Mingzhu Li for their kind help in the measurement of the reflection spectra of the perovskite@TiO2 NB array.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Qi L conceived the study. Wang W designed and performed the experiments. He Y participated in the materials preparation and data analysis. Wang W and Qi L wrote the manuscript. Qi L supervised the project. All authors contributed to the general discussion.

Author information

Wenhui Wang received her PhD degree in physical chemistry from Peking University under the supervision of Prof. Limin Qi in 2018. Currently, she is working at National University of Singapore as a research fellow. Her present research interests focus on the in-situ growth and assembly of metal nanoparticles using liquid cell TEM.

Limin Qi received his PhD degree from Peking University in 1998. He then went to the Max Planck Institute of Colloids and Interfaces as a postdoctoral fellow. In 2000, he joined the College of Chemistry at Peking University, where he has been a full professor since 2004. His research interests include colloidal chemistry, nanomaterials, self-assembly, energy-related materials, and biomimetic materials chemistry.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Brenner TM, Egger DA, Kronik L, et al. Hybrid organic-inorganic perovskites: low-cost semiconductors with intriguing charge-transport properties. Nat Rev Mater, 2016, 1: 15007 CrossRef ADS Google Scholar

[2] Chen H, Ye F, Tang W, et al. A solvent- and vacuum-free route to large-area perovskite films for efficient solar modules. Nature, 2017, 550: 92-95 CrossRef PubMed ADS Google Scholar

[3] Tan H, Jain A, Voznyy O, et al. Efficient and stable solution-processed planar perovskite solar cells via contact passivation. Science, 2017, 355: 722-726 CrossRef PubMed ADS Google Scholar

[4] Rong Y, Hu Y, Mei A, et al. Challenges for commercializing perovskite solar cells. Science, 2018, 361: eaat8235 CrossRef PubMed Google Scholar

[5] Jeon NJ, Na H, Jung EH, et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat Energy, 2018, 3: 682-689 CrossRef ADS Google Scholar

[6] Noh JH, Im SH, Heo JH, et al. Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. Nano Lett, 2013, 13: 1764-1769 CrossRef PubMed ADS Google Scholar

[7] Eperon GE, Burlakov VM, Goriely A, et al. Neutral color semitransparent microstructured perovskite solar cells. ACS Nano, 2014, 8: 591-598 CrossRef PubMed Google Scholar

[8] Jiang Y, Luo B, Jiang F, et al. Efficient colorful perovskite solar cells using a top polymer electrode simultaneously as spectrally selective antireflection coating. Nano Lett, 2016, 16: 7829-7835 CrossRef PubMed ADS Google Scholar

[9] Calvo ME. Materials chemistry approaches to the control of the optical features of perovskite solar cells. J Mater Chem A, 2017, 5: 20561-20578 CrossRef Google Scholar

[10] Stranks SD, Snaith HJ. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat Nanotech, 2015, 10: 391-402 CrossRef PubMed ADS Google Scholar

[11] Ergen O, Gilbert SM, Pham T, et al. Graded bandgap perovskite solar cells. Nat Mater, 2017, 16: 522-525 CrossRef PubMed ADS Google Scholar

[12] Cui D, Yang Z, Yang D, et al. Color-tuned perovskite films prepared for efficient solar cell applications. J Phys Chem C, 2016, 120: 42-47 CrossRef Google Scholar

[13] Esfandyarpour M, Garnett EC, Cui Y, et al. Metamaterial mirrors in optoelectronic devices. Nat Nanotech, 2014, 9: 542-547 CrossRef PubMed ADS Google Scholar

[14] Brongersma ML, Cui Y, Fan S. Light management for photovoltaics using high-index nanostructures. Nat Mater, 2014, 13: 451-460 CrossRef PubMed ADS Google Scholar

[15] Yang X, Wu J, Liu T, et al. Patterned perovskites for optoelectronic applications. Small Methods, 2018, 2: 1800110 CrossRef Google Scholar

[16] Deng Y, Wang Q, Yuan Y, et al. Vividly colorful hybrid perovskite solar cells by doctor-blade coating with perovskite photonic nanostructures. Mater Horiz, 2015, 2: 578-583 CrossRef Google Scholar

[17] Meng K, Gao S, Wu L, et al. Two-dimensional organic-inorganic hybrid perovskite photonic films. Nano Lett, 2016, 16: 4166-4173 CrossRef PubMed ADS Google Scholar

[18] Quiroz COR, Bronnbauer C, Levchuk I, et al. Coloring semitransparent perovskite solar cells via dielectric mirrors. ACS Nano, 2016, 10: 5104-5112 CrossRef Google Scholar

[19] Lee KT, Jang JY, Park SJ, et al. Incident-angle-controlled semitransparent colored perovskite solar cells with improved efficiency exploiting a multilayer dielectric mirror. Nanoscale, 2017, 9: 13983-13989 CrossRef PubMed Google Scholar

[20] Lu JH, Yu YL, Chuang SR, et al. High-performance, semitransparent, easily tunable vivid colorful perovskite photovoltaics featuring Ag/ITO/Ag microcavity structures. J Phys Chem C, 2016, 120: 4233-4239 CrossRef Google Scholar

[21] Lee KT, Fukuda M, Joglekar S, et al. Colored, see-through perovskite solar cells employing an optical cavity. J Mater Chem C, 2015, 3: 5377-5382 CrossRef Google Scholar

[22] Zhang W, Anaya M, Lozano G, et al. Highly efficient perovskite solar cells with tunable structural color. Nano Lett, 2015, 15: 1698-1702 CrossRef PubMed ADS Google Scholar

[23] Lee KT, Jang JY, Zhang J, et al. Highly efficient colored perovskite solar cells integrated with ultrathin subwavelength plasmonic nanoresonators. Sci Rep, 2017, 7: 10640 CrossRef PubMed ADS Google Scholar

[24] Liu D, Wang L, Cui Q, et al. Planar metasurfaces enable high-efficiency colored perovskite solar cells. Adv Sci, 2018, 5: 1800836 CrossRef PubMed Google Scholar

[25] Lee KT, Jang JY, Ha NY, et al. High-performance colorful semitransparent perovskite solar cells with phase-compensated microcavities. Nano Res, 2018, 11: 2553-2561 CrossRef Google Scholar

[26] Ye X, Qi L. Two-dimensionally patterned nanostructures based on monolayer colloidal crystals: Controllable fabrication, assembly, and applications. Nano Today, 2011, 6: 608-631 CrossRef Google Scholar

[27] Wang WH, Qi LM. Light Management with Patterned Micro- and nanostructure arrays for photocatalysis, photovoltaics, and optoelectronic and optical devices. Adv Funct Mater, 2019, 355: 1807275 CrossRef Google Scholar

[28] Vogel N, Retsch M, Fustin CA, et al. Advances in colloidal assembly: The design of structure and hierarchy in two and three dimensions. Chem Rev, 2015, 115: 6265-6311 CrossRef PubMed Google Scholar

[29] Wang W, Jin C, Qi L. Hierarchical CdS nanorod@SnO2 nanobowl arrays for efficient and stable photoelectrochemical hydrogen generation. Small, 2018, 14: 1801352 CrossRef PubMed Google Scholar

[30] Arain Z, Liu C, Yang Y, et al. Elucidating the dynamics of solvent engineering for perovskite solar cells. Sci China Mater, 2019, 62: 161-172 CrossRef Google Scholar

[31] Zheng H, Dai S, Zhou K, et al. New-type highly stable 2D/3D perovskite materials: the effect of introducing ammonium cation on performance of perovskite solar cells. Sci China Mater, 2019, 62: 508-518 CrossRef Google Scholar

[32] Shao J, Guo X, Shi N, et al. Acenaphthylene-imide based small molecules/TiO2 bilayer as electron-transporting layer for solution-processing efficient perovskite solar cells. Sci China Mater, 2019, 62: 497-507 CrossRef Google Scholar

[33] Liu J, Li N, Dong Q, et al. Tailoring electrical property of the low-temperature processed SnO2 for high-performance perovskite solar cells. Sci China Mater, 2019, 62: 173-180 CrossRef Google Scholar

[34] Wang W, Ma Y, Qi L. High-performance photodetectors based on organometal halide perovskite nanonets. Adv Funct Mater, 2017, 27: 1603653 CrossRef Google Scholar

[35] Huang F, Pascoe AR, Wu WQ, et al. Effect of the microstructure of the functional layers on the efficiency of perovskite solar cells. Adv Mater, 2017, 29: 1601715 CrossRef PubMed Google Scholar

[36] Zhao Y, Zhu K. Organic–inorganic hybrid lead halide perovskites for optoelectronic and electronic applications. Chem Soc Rev, 2016, 45: 655-689 CrossRef PubMed Google Scholar

[37] Hörantner MT, Zhang W, Saliba M, et al. Templated microstructural growth of perovskite thin films via colloidal monolayer lithography. Energy Environ Sci, 2015, 8: 2041-2047 CrossRef Google Scholar

[38] Zheng X, Wei Z, Chen H, et al. Designing nanobowl arrays of mesoporous TiO2 as an alternative electron transporting layer for carbon cathode-based perovskite solar cells. Nanoscale, 2016, 8: 6393-6402 CrossRef PubMed ADS Google Scholar

[39] Hu X, Huang Z, Zhou X, et al. Wearable large-scale perovskite solar-power source via nanocellular scaffold. Adv Mater, 2017, 29: 1703236 CrossRef PubMed Google Scholar

[40] Wang W, Dong J, Ye X, et al. Heterostructured TiO2 nano-rod@nanobowl arrays for efficient photoelectrochemical water splitting. Small, 2016, 12: 1469-1478 CrossRef PubMed Google Scholar

[41] Yoon KY, Ahn HJ, Kwak MJ, et al. A selectively decorated Ti-FeOOH co-catalyst for a highly efficient porous hematite-based water splitting system. J Mater Chem A, 2016, 4: 18730-18736 CrossRef Google Scholar

[42] Lee JW, Kim HS, Park NG. Lewis acid–base adduct approach for high efficiency perovskite solar cells. Acc Chem Res, 2016, 49: 311-319 CrossRef PubMed Google Scholar

[43] Zhang W, Saliba M, Moore DT, et al. Ultrasmooth organic-inorganic perovskite thin-film formation and crystallization for efficient planar heterojunction solar cells. Nat Commun, 2015, 6: 6142 CrossRef PubMed ADS Google Scholar

[44] Jeon NJ, Noh JH, Kim YC, et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat Mater, 2014, 13: 897-903 CrossRef PubMed ADS Google Scholar

[45] Pham ND, Tiong VT, Chen P, et al. Enhanced perovskite electronic properties via a modified lead(II) chloride Lewis acid–base adduct and their effect in high-efficiency perovskite solar cells. J Mater Chem A, 2017, 5: 5195-5203 CrossRef Google Scholar

[46] Zhang T, Guo N, Li G, et al. A controllable fabrication of grain boundary PbI2 nanoplates passivated lead halide perovskites for high performance solar cells. Nano Energy, 2016, 26: 50-56 CrossRef Google Scholar

[47] Liu FZ, Dong Q, Wong MK, et al. Is excess PbI2 beneficial for perovskite solar cell performance?. Adv Energy Mater, 2016, 6: 1502206 CrossRef Google Scholar

[48] Jiang Q, Chu Z, Wang P, et al. Planar-structure perovskite solar cells with efficiency beyond 21%. Adv Mater, 2017, 29: 1703852 CrossRef PubMed Google Scholar

[49] He YT, Wang WH, Qi LM. HPbI3 as a bifunctional additive for morphology control and grain boundary passivation toward efficient planar perovskite solar cells. ACS Appl Mater Interfaces, 2018, 10: 38985-38993 CrossRef Google Scholar

[50] Rong Y, Tang Z, Zhao Y, et al. Solvent engineering towards controlled grain growth in perovskite planar heterojunction solar cells. Nanoscale, 2015, 7: 10595-10599 CrossRef PubMed ADS Google Scholar

[51] Green MA, Ho-Baillie A, Snaith HJ. The emergence of perovskite solar cells. Nat Photon, 2014, 8: 506-514 CrossRef ADS Google Scholar

[52] Xia Y, Ran C, Chen Y, et al. Management of perovskite intermediates for highly efficient inverted planar heterojunction perovskite solar cells. J Mater Chem A, 2017, 5: 3193-3202 CrossRef Google Scholar

[53] Cao XB, Li YH, Fang F, et al. High quality perovskite films fabricated from Lewis acid–base adduct through molecular exchange. RSC Adv, 2016, 6: 70925-70931 CrossRef Google Scholar

[54] Zuo L, Gu Z, Ye T, et al. Enhanced photovoltaic performance of CH3NH3PbI3 perovskite solar cells through interfacial engineering using self-assembling monolayer. J Am Chem Soc, 2015, 137: 2674-2679 CrossRef PubMed Google Scholar

[55] Bi C, Wang Q, Shao Y, et al. Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat Commun, 2015, 6: 7747 CrossRef PubMed ADS Google Scholar

[56] Zhang W, Pathak S, Sakai N, et al. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells. Nat Commun, 2015, 6: 10030 CrossRef PubMed ADS Google Scholar

[57] Kolle M, Salgard-Cunha PM, Scherer MRJ, et al. Mimicking the colourful wing scale structure of the Papilio Blumei butterfly. Nat Nanotech, 2010, 5: 511-515 CrossRef PubMed ADS Google Scholar

[58] Diao YY, Liu XY, Toh GW, et al. Multiple structural coloring of silk-fibroin photonic crystals and humidity-responsive color sensing. Adv Funct Mater, 2013, 23: 5373-5380 CrossRef Google Scholar

[59] Umh HN, Yu S, Kim YH, et al. Tuning the structural color of a 2D photonic crystal using a bowl-like nanostructure. ACS Appl Mater Interfaces, 2016, 8: 15802-15808 CrossRef Google Scholar

[60] Si H, Liao Q, Zhang Z, et al. An innovative design of perovskite solar cells with Al2O3 inserting at ZnO/perovskite interface for improving the performance and stability. Nano Energy, 2016, 22: 223-231 CrossRef Google Scholar

[61] Li W, Zhang W, Van Reenen S, et al. Enhanced UV-light stability of planar heterojunction perovskite solar cells with caesium bromide interface modification. Energy Environ Sci, 2016, 9: 490-498 CrossRef Google Scholar

Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有