Scalable Fabrication of Metal Halide Perovskite ... - ACS Publications

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Upscalable Fabrication of Metal Halide Perovskite Solar Cells and Modules Longbin Qiu, Sisi He, Luis K Ono, Shengzhong (Frank) Liu, and Yabing Qi ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.9b01396 • Publication Date (Web): 02 Aug 2019 Downloaded from pubs.acs.org on August 3, 2019

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ACS Energy Letters

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Upscalable Fabrication of Metal Halide Perovskite

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Solar Cells and Modules

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Longbin Qiu 1,†, Sisi He 1,†, Luis K. Ono 1,†, Shengzhong Liu 2,3,*, Yabing Qi 1,*

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1

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Technology Graduate University (OIST), 1919-1 Tancha, Onna-son, Kunigami-gun, Okinawa

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904-0495, Japan.

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2

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Chinese Academy of Sciences, 457 Zhongshan Road, 116023 Dalian, China.

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3

Energy Materials and Surface Sciences Unit (EMSSU), Okinawa Institute of Science and

Dalian National Laboratory for Clean Energy, iChEM, Dalian Institute of Chemical Physics,

Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Shaanxi Key

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Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy

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Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an

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710119, China.

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AUTHOR INFORMATION

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Corresponding Author

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* E-mail: [email protected] (Y.B.Q.); [email protected] (S. L.).

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†These authors contributed equally to this work.

1 ACS Paragon Plus Environment

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ABSTRACT

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Perovskite photovoltaic (PV) technology towards commercialization relies on high power

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conversion efficiency (PCE), long lifetime, and low-toxicity in addition to development of

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upscalable fabrication protocols, optimization of large area solar module structures, and a positive

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cost-benefit assessment. Although small area metal halide perovskite solar cells (PSCs) show PCE

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up to 24.2%, the efficiency gap between small and large area PSC devices is still large. Worldwide

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research efforts have been directed towards developing upscalable fabrication strategies for

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perovskite solar modules. In this perspective, we share our view regarding the current-stage

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challenges for the fabrication of perovskite solar modules with areas above 200 cm2 and

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summarize recent progress in minimizing efficiency gap, and highlight what strategies warrant

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further investigation for moving perovskite PV technology towards industrial scale. These

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strategies include learning from other commercialized thin film PV technologies, analyzing the

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current status on perovskite solar modules employing solution- and vapor-based upscalable

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fabrication techniques and optimizing large area module designs. Considering cost analysis and

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operational stability profiles, carbon electrode-based devices are particularly promising.

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TOC GRAPHICS

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ACS Energy Letters

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Solar energy is recognized as one of the most promising renewable energy sources because of

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its cleanness, abundance, easiness to operate, quietness in the sense that moving mechanical parts

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are not a requisite, and being safe.1 In addition, it has the advantage of capability to cover a wide

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range of power generation capacity ranging from milliwatt (mW) to multi-gigawatt (GW). For

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example, large scale PV power stations (or solar farms) can be designed to power cities and

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industries,2 while at the same time stand-alone systems can be employed in terrestrial isolated rural

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zones and space programs to power satellites. PVs with compact and light-weight characteristics

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can also be designed for operating small electronics that require low-power (e.g., portable

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electronics, smart-phone battery charging, internet of things, and so on). Therefore, the size and

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configuration of a PV system can be designed to satisfy the energy demand for a specific

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application.3 In March of 2019, the National Renewable Energy Laboratory (NREL) released the

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“Champion Photovoltaic Module Efficiency Chart”.4 This new chart is devoted specifically to the

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development of solar modules, which differs from the champion laboratory-scale (small sizes)

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research-cell efficiency chart.5 The chart of power conversion efficiencies (PCEs) of solar modules

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allows researchers and industry to gain insight into the progress and trends of different PV

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technologies in the context of upscalable fabrication. The modules are categorized into four

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clusters delineated by the total module area size, which includes both the active area and the dead

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areas needed for module interconnections.6-7 For a solar module to be included in either of NREL

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solar module efficiency chart4 or (solar cell efficiency tables provided by Prof. Martin Green and

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coworkers),8 (i) the active area efficiency is not a consideration and (ii) the relevant designated or

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aperture area for submodule need be in the smallest range of 200-800 cm2. As listed below, in the

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NREL chart, the sizes are divided into 4 categories, while only 2 categories exist in the solar cell

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efficiency table provided by Prof. Martin Green et. al.



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Solar module efficiency chart classification (NREL):4,9

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Large module: >14,000 cm2

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Standard module: 6,500–14,000 cm2

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Small module: 800–6,500 cm2

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Mini or sub-module: 200–800 cm2

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Solar cell efficiency tables (Prof. Martin Green and coworkers)8

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module: over 800 cm2

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sub-module: 200–800 cm2

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This chart summarizes a variety of state-of-the-art PV materials and technologies, which were

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developed in the last few decades with the aim to achieve the highest performance for harvesting

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solar energy at the lowest production cost.4, 8 Among these various types of PV technologies (e.g.,

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Si, CIGS, CdTe, etc.),10-11 metal halide perovskites (denoted as “perovskites” throughout the article)

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have recently gained considerable attention, and are considered as a strong candidate for the next

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generation of solar cells and modules because of their excellent photovoltaic properties, raw

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material abundance, low-cost and low-temperature fabrication, compatibility with flexible

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substrates, etc. On the basis of our analysis represented in Figure 1 and Table 1, there are only a

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few works that reported perovskite solar modules with areas larger than 200 cm2. Although

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feasibility for the realization of perovskite solar modules with areas larger than 10 cm2 and PCE

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above 10% has been demonstrated, these solar module area sizes are still far from the expected

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200 cm2. Therefore, several issues need be overcome and we share a few strategies based on our

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own experience as well as some knowledge learned from other research groups in the field. For


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example, these strategies include (i) borrowing the processes from other commercialized thin film

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PV technologies, (ii) analyzing the key issues in the fabrication process of solution- and vapor-

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based upscalable techniques with emphasis on the chemical vapor deposition technology, and (iii)

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the past experience on optimizing the module patterning design.

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Currently, Toshiba Corporation holds the world record for the largest CH3NH3PbI3 (MAPbI3)

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perovskite film-based PV sub-module with 24.15 cm ´ 29.10 cm (703 cm2 designated illumination

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area; definitions of the measurement areas can be found from references7-8) with a certified PCE

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of 11.7%, open circuit voltage (Voc) of 1.073 V, short circuit current density (Jsc) of 14.36

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mA/cm2, and fill factor (FF) of 75.8% (here all the Voc and Jsc are given or calculated according

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to the value of per cell in the module. The aim is to make it more convenient to compare with other

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works about module as different modules have different number of cells in series connection).12

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To further enlarge the area from 703 cm2 to 802 cm2, a perovskite solar module with certified PCE

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of 11.6% has been achieved (Figure 1).8 This large-area sub-module and module were fabricated

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by a 2-step process employing the meniscus printing technology with the PbI2 and CH3NH3I

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precursor solutions applied sequentially. It has been mentioned that the goal of the company is to

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fabricate PV modules with sizes of 900 cm2 that would be possible to achieve a levelized cost of

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electricity of ~0.06 USD (7 JPY) per kWh by 2030.12 In this perspective, we analyze the current

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progress of solution- and vapor-based upscalable techniques that allowed fabrication of solar

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modules with a total area larger than 10 cm2. On the basis of our analysis (Table 1 and Figure 1),

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we provide our views on the major challenges needed to be overcome to successfully minimize

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the efficiency gap (i.e., the difference in the performance between small cells and larger module

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scales).13-14 The first challenge is related to preparation of high quality (i.e., uniform coverage and



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chemical composition, high-crystallinity, and low surface roughness over the large area) and

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reproducible films of perovskites as well as compatibility with adjacent functional layers forming

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the whole perovskite solar module. The second challenge is related to the needs to optimize solar

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module design for attaining high performance. It is important to minimize the effects of the sheet

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resistance to facilitate charge collection by the electrodes. The third challenge concerns the

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fabrication-cost issues during development of upscaling. Carbon electrode-based devices have the

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potential to lower the fabrication cost and enhance the solar module operational stability. In the

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outlook, we propose further research directions that have been developed in small lab-scale solar

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cells and discuss the potential and how these strategies could be transferred in the development of

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solar modules.

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Figure 1. Summary plots of the solar module parameters (a) PCE, (b) Jsc, (c) Voc, and (d) FF that

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show current progress employing different upscalable techniques of solution-based (spin-coating,

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doctor-blading, slot-die, meniscus, screen printing) and vapor-based methods (HCVD, CVD, and

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CH3NH2-gas treatment). In these plots, we included published works reporting perovskite solar

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modules that employ series-interconnections and with a total area larger than 10 cm2 (see Table

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1). PCE, Voc, and Jsc values are normalized according to the active area and the number of

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interconnected cells. Jsc in (b) is calculated to be the current density passing of each cell multiplied

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by the number of interconnected cells. Voc in (c) is calculated to be the total open circuit voltage

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of the solar module divided by the number of interconnected cells. The horizontal dashed-line

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corresponds to the highest certified small cell efficiency that have been published.15 The

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highlighted zone above 200 cm2 corresponds to the minimum size that is needed to be considered

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as mini- or sub-module in the NREL “Champion Module Efficiencies” chart.4

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The progress of solution-based upscalable techniques. The first perovskite solar module

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employed the spin-coating technique leading to a PCE of 5.1% with an active area of 16.8 cm2

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(the total substrate size = 25 cm2).16-18 During the past few years, remarkable progress towards

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upscaling of perovskite solar modules can be clearly seen based on a survey of selected papers

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employing solution techniques to fabricate solar modules with a total area larger than 10 cm2

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(Table 1). To evaluate the progress and whether perovskite solar modules show promises for

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attaining higher efficiencies when made larger, we have generated summary graphs that show not

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only the PCE, but also all the solar cell parameters (Jsc, Voc, FF) plotted as a function of solar

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module active area (Figure 1). From these graphs, it can be inferred that great efforts for upscaling

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of perovskite solar modules have been done employing spin-coating (17 out of 40 studies surveyed

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in this review) as it is most common and readily available in the laboratories working with lab-



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scale small area perovskite solar cell (PSC) devices.16, 19-26 As a reference to illustrate the efficiency

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gap,13-14 we also plot the published values of the certified small area PSC performance (PCE =

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23.32%, Jsc = 25.2 mA/cm2, Voc = 1.18 V, FF = 78.4%, active area = 0.0739 cm2) reported by

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You and coworkers.15 and indicated these values as horizontal dashed-lines in Figure 1a-d. Spin-

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coating has been demonstrated to generate PCEs as high as ~13% with a reported active area size

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of 50.6 cm2 (on a total substrate area of 100 cm2).19 Spin-coating is a low-cost and easy-to-operate

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technique, but it is challenging to use this technique to deposit uniform films of perovskites in a

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reproducible manner when the sizes are larger than 100 cm2. Hence, several solution-based

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methods (Figure 2) that are more compatible with upscalable fabrication have been developed,

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such as blade-coating,27-31 slot-die coating,32-36 meniscus assisted solution printing,37 screen-

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printing,38-39 spray-coating,34, 40-41 soft-cover deposition,41-42 pressure processing method,43 and

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inkjet printing.44-46 Although the number of publications is still small, it is possible to observe

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some trends from these reports. Among all these upscalable solution-based methods listed above,

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and screen printing (4 out of 40 studies)38-39, 47-48, blade-coating (3 out of 40 studies surveyed in

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this work),27-28, 31 and slot-die coating (3 out of 40 studies)33, 36, 49 have attracted more attention.

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On the other hand, meniscus printing (2 out of 40 studies)12, 50 and spray-coating (1 out of 40

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studies)41 are also promising. On the basis of Figure 1, the feasibility has been demonstrated for

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the realization of perovskite solar modules with areas larger than 10 cm2 and PCE above 10%.7, 48,

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51-52

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pin-hole free perovskite films with large grains, high-crystallinity, and uniform stoichiometry

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across large areas. The understanding and control of the physico-chemical dynamics during film

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growth, which are strongly dependent on the different coating processes and solution precursor,

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are requisites for attaining high quality perovskite films.

Currently one of the most challenging issues is the need to reproducibly deposit smooth and


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The coating processes employing spin-coating has been well-characterized. For a solution

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coating process that employs upscalable technique (for instance blade coating), one may consider

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that similar nucleation and crystal growth dynamical processes take place in the blade coating

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compared to that of spin-coating. However, a key aspect in the perovskite one-step coating process

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is the need to rapidly remove the solvent during drying of the film. The anti-solvent

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dripping/washing process,27-28 which promotes the rapid removal of solvent during film drying, is

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feasible for spin-coating but challenging for other solution-based upscalable methods. The solution

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chemistry need be modified and optimized according to the specific upscalable coating process.27-

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28

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instruments. In spin-coating, the substrate is rotated at a high speed in order to efficiently spread

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the extra solution out from the film by the aid of centrifugal force. In contrast, all other upscalable

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techniques are based on non-rotating coating techniques.27-28 Therefore, development of precursor

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solutions is a key factor when employing non-rotating coating techniques because the physical

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properties of the solvent-drying processes influence significantly the final film quality.28, 53 Several

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strategies of precursor ink formulation modification have been proposed in one-step method such

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as (i) surfactant-controlled (for example, L-α-phosphatidylcholine) ink drying process with doctor

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blading;27 (ii) blade coating with MACl additive to optimize crystal growth;28 (iii) air blow or

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vacuum flash-assisted solution process.33,

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processes such as inter-diffusion process and sequential coating of two precursor inks with

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upscalable techniques were reported.54-55 Currently, the largest certified solar module held by

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Toshiba Corporation employed a two-step coating process.12 Another promising direction is the

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development of new chemical processes. For instance, Han and coworkers43 developed the amine

Another aspect relates to the differences in the technical aspects of spin-coating and upscaling

49

Alternatively, two-step perovskite film formation



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complex precursors of CH3NH3I ⋅ mCH3NH2 and PbI2 ⋅ nCH3NH2 for fabrication of MAPbI3

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perovskite films. The ink formulation was optimized to be used in their pressure processing method.

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In this technique, the uniform spreading of the liquid precursor on the substrate is performed by

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applying a pneumatically driven pressure with a polyimide coated flat squeezing board. CH3NH2

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gas evaporates leading to a dense and full coverage MAPbI3 perovskite film. Furthermore, a

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certified PCE of 12.1% has been reported based on a MAPbI3 perovskite solar module with an

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aperture area of 36.1 cm2. At the current stage the aforementioned processes employed mainly

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MAPbI3 perovskite, and further efforts are needed to develop suitable precursor solutions and

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chemistry processes for upscalable fabrication of PSCs based on mixed-cation and halide

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perovskites with better stability and / or photoelectronic properties. More detailed descriptions

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about these upscalable methods can be found from several review articles.6-7, 51-52, 56-69 In the next

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section, we discuss vapor-based methods that have shown some initial success as an attracting

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alternative to fabricate perovskite solar modules.


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Figure 2. Schematic drawing showing the important route from developing protocols employing

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upscalable (a) solution and (b) vacuum based coating techniques to perovskite solar module design

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and commercialization. State-of-the-art perovskite solar modules can be fabricated by solution

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coating processes or vapor deposition processes. There are two common solar module architectures,

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i.e., (c) series connection and (d) parallel connection. (e) For commercialization, the cost and



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installation need be taken into consideration. This pie chart summarizes the cost distribution for a

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typical perovskite solar module. (f) The perovskite solar farm image reprinted with permission

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from ref. 13. Copyright 2018 American Association for the Advancement of Science (AAAS).

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The progress of vapor-based upscalable techniques. Vapor-based methods have also been

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demonstrated as a promising route for the fabrication of perovskite PV modules. In the field of

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thin-film PV technology, the highest efficiencies in Cu(In,Ga)Se2 (CIGS) PV devices are

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fabricated by physical vapor deposition (PVD) (vacuum co-evaporation or sequential inline

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deposition), and the constituent-component vapors are condensed onto the substrates with Mo as

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back contact.70-71 Similarly, highly efficient CdTe-based PV devices are fabricated by the so-called

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vapor transportation deposition (VTD) and close-spaced sublimation (CSS) techniques, both of

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which can be regarded as PVD.72-77 The design prerequisite for PVD-based equipment is to

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minimize the influence of extrinsic impurities that may be incorporated from uncontrolled ambient

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during film deposition. Chemical vapor deposition (CVD) is another mature vapor-based method

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that has been playing a pivotal role in Si-based PV industry.78 In fact, former United Solar Ovonic

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LLC used to fabricate triple-junction thin film silicon cells using roll-to-roll PECVD technology,

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with each run producing 15 kilometer-long solar cells.79-80

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In a broad context, a CVD process refers to the formation of a thin solid film on a substrate via

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a chemical reaction of vapor-phase precursors and therefore it differs from PVD. CVD has been

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widely employed in PV sector and industrial settings, e.g., Mitsubishi Heavy Industries, Ltd

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demonstrated operating megawatt capacity solar farm based on single junction hydrogenated

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amorphous Si (a-Si:H) solar modules grown by plasma enhanced CVD installed in Germany.81-82

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Another area where PECVD has been extensively employed is the deposition of an a-Si:H


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passivation layer in c-Si solar cells. The a-Si:H layer is a key to passivating Si dangling bonds. In

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2017, the Kaneka R&D group applied (i) the passivating-contact solar cell technology and (ii)

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interdigitated back contact technology, which helped set the world’s Si single junction solar cell

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efficiency record of 26.6% with a designated area of 180.4 cm2.83-84 CVD has also be used in

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depositing transparent conductive oxide (TCO) such as SnO2, F-doped SnO2 (FTO), and ZnO85-86

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as well as antireflection (AR) coatings87-88 such as SiN, SiO2, and TiO2. Vapor-based methods

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have the advantage of low-cost and high-throughput, which have been already widely adopted in

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the coating and semiconductor industry.89 Hence fabrication of solar modules based on all vapor

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methods (i.e., solvent-free processes) could be also envisaged for the perovskite PV technology.57,

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90-93

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There have been some demonstrations to employ vapor-based methods in PSCs. In addition to

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uniform film formation across large areas, there are also other unique advantages for vapor-based

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processes compared with solution coating processes such as easy formation of perovskite

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heterojunction structures94 and conformal coating in textured-structured surfaces.95 These vapor-

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based processes for perovskite can be summarized as co-evaporation of organic and inorganic

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precursors (PVD),96-97 alternating precursor deposition,98 direct contact deposition,99 hybrid CVD

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(HCVD),100-101 reactive polyiodide melts process,102 vapor assisted solution process (VASP),103

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CSS104 and recently reported sputtering deposition105. Since Qi and coworkers101 developed the

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HCVD technique and demonstrated efficient PSCs, a variety of CVD techniques were

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consecutively invented showing outstanding achievements in perovskite PV technology.91

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Although there are more and more research works on vapor-based processes for PSCs, the number

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of works focusing on vapor-based methods is still small compared to that of the works focusing



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on solution-based methods. Furthermore, only a very few works have been published in applying

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vapor-based methods in perovskite solar modules with larger areas. Among various vapor-based

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methods (Table 1), HCVD is particularly promising in upscaling perovskite solar modules. HCVD

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is a thin-film deposition method that combines PVD and CVD. A multi-zone furnace with flexible

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control of growth parameters (carrier gas, pressure, and temperature) is used in the HCVD process.

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Typically, perovskite film growth by HCVD process is a two-step process (Figure 2). This has the

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advantage that the individual steps can be optimized individually. In the first step, optimization

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and coating of inorganic precursors (e.g., PbI2, PbCl2, CsI, etc.) are coated by vacuum evaporation

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or upscalable solution techniques. Subsequently, the inorganic precursor coated films are

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transferred into a tube furnace equipped with temperature controller and pressure gauge used to

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optimize the organic halide vapor (e.g., MAI, FAI, MABr, FABr, etc.). The organic halide vapor

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deposits on the PbI2/PbCl2 films followed by the inter-diffusion into the films leading to the

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conversion of uniform perovskite layers. Perovskite growth by HCVD was first demonstrated in

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2014.101, 106-107, and the first perovskite solar module by HCVD was demonstrated in 2016.100 At

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present most of the vapor-based perovskite solar modules are fabricated by HCVD. In the context

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of PSC research, CVD has the particular advantages such as (i): CVD is a mature and well-

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established technology in the semiconductor and coating industries. CVD is not only compatible

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with industrial application for large scale commercial processes, but also has the ability of batch

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process and high throughput continuous processes as proven by manufacturers in their kilometer-

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long roll-to-roll deposition.79-80 In addition, the vacuum processes are easy for patterning,

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compatibility with a wide range of materials, reasonable capital investment, and cost-effectiveness

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of processing; (ii) vapor deposition eliminates the usage of harmful organic solvents55, 108-112 and

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reduces the wastes of perovskite precursor solutions. Hence, CVD represents a low environmental


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impact processing method. In addition, it avoids the complications of solvent related dynamics

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such as solubility of the bottom layer when covered by the precursor solution of the top film,

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intercalation of solvent molecules into the solid material, wettability issues leading to non-uniform

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coating; (iii) weak dependence on substrate size meaning that the perovskite films can be coated

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uniformly on substrates with almost arbitrary large sizes and with varying aspect ratios, limited

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only by the CVD apparatus size; (iv) such a coating process can be directly applied in two-terminal

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tandem solar cells with a perovskite layer as a top cell and silicon, CIGS or CdTe as the bottom

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cell. In addition, the vapor nature of CVD allows the deposition of a type of perovskite on top of

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another perovskite (for example, forming a p-n homojunction structure). Perovskite solar modules

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with active areas over 10 cm2 fabricated by vapor-based methods have also been included in Table

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1. As we can see, all the works used HCVD except one study by Qi and coworkers.113 Recently, a

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remarkable large area solar modules with mixed Cs/FA cation deposited by HCVD have been

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demonstrated with efficiencies approaching 10% with a designated area of 91.8 cm2, which were

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fabricated on 10 cm ´ 10 cm substrates.114 Most importantly, the performance decay with upscaling

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of active area is similar to other commercialized thin film solar modules (1.3%/decade compared

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with 0.8%/decade; Figure 1).114

289 290

Although HCVD is the dominant method for fabricating most of the reported perovskite solar

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modules using vapor-based methods, there are other new trends we can learn from the recent

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progress in the field. The strategies of mixing two or more cations and / or mixing halides have

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been demonstrated to be beneficial in tuning optoelectronic properties of perovskite materials as

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well as enhancing their stability.115 Similar to solution coating processes, the perovskite

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composition can be tuned by changing the precursor sources. For example, Bolink and coworkers



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reported fabrication of triple-cation mixed-halide small-area PSCs (active area = 0.09 cm2) by

297

vacuum deposition116 and co-evaporation to incorporate Cs in the first step were previously

298

reported.95, 114, 117 Another strategy is to combine solution and vapor processes and it shows unique

299

advantages over solution-only processes.118-119 Recently many high performance PSCs have been

300

reported by the two-step inter-diffusion method of solution-processed precursor stacking layers.15,

301

54

302

mixed organic halide salt solution requires uniform coating of the solution and removal of solvent

303

in the whole area in a short time.119 This is easy to control for lab-scale small device fabrication

304

processes but difficult for industrial large scale fabrication. Furthermore, in vapor-based processes,

305

the slower reaction and uniform coating of the halide salts are beneficial for the growth of uniform

306

perovskite films. By optimizing the first step of metal halide solution composition, not only the

307

composition of the as-formed perovskite film, but also the structural properties could be readily

308

modified. Another example to combine solution and vapor methods is the study by Qi and

309

coworkers, in which a solid-gas reaction between the MACl modified HPbI3 (pre-deposited by

310

spin-coating) and CH3NH2 gas leads to formation of high-quality over 1.1 µm thick MAPbI3 films

311

resulting in perovskite solar modules with a PCE of 15.3% on an active area size of 12 cm2.113

312

Similar to CVD process, CH3NH2 gas treatment is also a two-step process with the first step aiming

313

the optimized coating of HPbI3. Subsequent exposure of the HPbI3 coated substrates to CH3NH2

314

gas environment leads to the immediate formation of perovskite-melt. After the removal of

315

CH3NH2 gas, high quality perovskite films are obtained. CH3NH2 gas treatment is suitable for the

316

fabrication of high-quality thick perovskite films up to 1 µm.113 The encouraging device

317

performance and long-term operational stability profile represent to a promising direction of

However, for mixed cation/halide perovskite, the fast reaction in the second step after dropping


Page 17 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

318

employing thick absorber films to realize solar modules with high efficiencies, reproducibility,

319

and stability.

320 321

Table 1. Selected works reporting on perovskite solar modules that employs series-

322

interconnections and with total areas larger than 10 cm2. The PCE and Jsc values are provided

323

normalized by the active area unless otherwise stated: apaperture area, dadesignated area (active

324

area + dead area for interconnections).

325

b

CE

Certified efficiency. aNormalized by active area.

Stabilized PCE.

Solar module architecture ITO/PEDOT:PSS/MAPbI3/PCBM/LiF/Al FTO/c-TiO2/mp-TiO2/MAPbI3-xClx/spiroMeOTAD/Au FTO/c-TiO2/mp-TiO2/MAPbI3-xClx/P3HT/Au ITO/PEDOT:PSS/MAPbI3/PCBM/Au FTO/c-TiO2/nano rod-TiO2/CH3NH3PbI3xClx/spiro-MeOTAD/Au ITO/c-TiO2/mp-TiO2/CH3NH3PbI3-xClx/spiroMeOTAD/Au FTO/c-TiO2/mp-TiO2/MAPbI3/spiroMeOTAD/Au ITO/c-TiO2/MAPbI3-xClx/spiro-MeOTAD/Au ITO/PEDOT:PSS/CH3NH3PbI3-xyBrxCly/PCBM/Ca/Al

Perovskite fabrication method

Active area (cm2)

Spin-coating

60

Spin-coating

16.8

Total area Number of Individual (cm2) (lateral cells cell width PCEa dimensions interconne ´ length (%) cted (cm´cm)) (mm) 10 8.7 100 (10´10) 6´10 25 (5´5)

5

7´48

Jsca (mA/c m2)

Voc (V)

FF (%)

Ref.

1.9

8.1

57

16

5.1

2.0

4.3

60.3

2.2 2

4.5 10.1

52.6 63.7

26

18

Spin-coating

40

100 (10´10)

10

---

5.1 12.9

Spin-coating

10.8

32.5 (5.7´5.7)

4

---

10.5

5.3

3.37

56

120

Spin-coating

7.9

31.4 (5.6´5.6)

4

---

3.1

5.2

3.4

71

121

Spin-coating

10.1

32.5 (5.7´5.7)

4

7´36

13

4.7

4.2

66.5

17

Spin-coating

3.64

9 (3´3)

4

4.57´20

13.6

19.1

0.9/cell

75

122

Spin-coating

25.2

100 (10´10)

9

4´70

14.3

2.1

9.1

74.4

22

25 (5´5)

8

---

12

2.6

8

58.2

20

25 (5´5)

5

5´45

15.4

4.3

4.7

77

123

FTO/NiOx/MAPbI3-xClx/PCBM:PEI/Ag

Spin-coating

ITO/PEDOT:PSS/MAPbI3/PC71BM/Ca/Al FTO/c-TiO2/mpTiO2/Graphene/MAPbI3/Spiro-MeOTAD/Au ITO/PEDOT:PSS/MAPbI3xClx/PC61BM/TIPD/Al FTO/SnO2/KxCs0.05(FA0.85MA0.15)0.92Pb(I0.85B r0.15)3/spiro-MeOTAD/Au PET/ITO/SnO2/K0.03Cs0.05(FA0.85MA0.15)0.92Pb (I0.85Br0.15)3/spiro-MeOTAD/Au FTO/SnO2/MAPbI3/spiro-MeOTAD/Au FTO/SnO2/ [CsPbI3]0.05[(FAPbI3)0.85(MAPbBr3)0.15]0.95/ spiro-MeTOAD/Au FTO/c-TiO2/mp-TiO2 /(FAPbI3)0.95(MAPbBr3)0.05/WBH/P3HT/Au

Spin-coating

15 (GFF ~ 0.6) 11.25

Spin-coating

50.6

100 (10´10)

8

8´79

12.6

2.3

8.6

64.6

19

Spin-coating

12

25 (5´5)

3

30´40

11.2

6.5

2.7

63.8

124

Spin-coating

20

36 (6´6)

6

6´55

15.6

3.5

6.8

65

125

25 (5´5)

6

---

12.4

3.07

6.5

62

126

25 (5´5)

6

7.1´48

12.03

3.38

5.8

61.3

127

6.5´6.5

11

---

15.3

1.98

11.2

0.69

100da Spin-coating 24.94da

--49 (7´7)

20 8

-----

14.03 17.1da

1.02 2.72da

20.2 8.78

0.68 71.7

24.94da

49 (7´7)

8

---

17.1da

2.72da

8.66

72.6

16.1ap

30 (5´6)

6

---

15.2

3.28

6.7

69

130

100

176 (16´11)

9

---

4.3

7.5

9.6

53.8

31

PET/ITO/SnO2/Cs0.05(FA0.85MA0.15)0.95Pb(I0.85 Br0.15)3/spiro-MeOTAD/Au FTO/c-TiO2/mp-TiO2/MAPbI3/P3HT/Au

Spin-coating Spin-coating Spin-coating

Bar-coating Spin-coating / Slot-die coating (SnO2) Doctor blading

10

ap

22.4

da

25da

128 129



FTO/c-TiO2/MAPbI3/spiro-MeOTAD/Ag

Doctor blading

ITO/PTAA/MAPbI3/C60/BCP/Cu

Doctor blading

PET/ITO/ZnO/MAPbI3/P3HT/Ag FTO/ZnO/MAPbI3/Carbon ITO/c-TiO2/MAPbI3-xClx/SpiroMeOTAD/Au

MAPbI3 (Toshiba Corporate R&D Center)

Slot-die coating Slot-die coating Slot-die coating

Meniscus printing

11.1

24.2 (6.35´3.81)

33ap 57.2ap

Meniscus coating

FTO/c-TiO2/mp-ZrO2/MA(5AVA)PbI3/Carbon FTO/c-TiO2/(mp-TiO2/mpZrO2/mp-C)/(5AVA)x(MA)1-xPbI3 FTO/c-TiO2/(mp-TiO2/mpZrO2/mp-C)/(5AVA)x(MA)1-xPbI3

Screen printing Screen printing Screen printing

FTO/c-TiO2/(mp-TiO2/mpZrO2/mp-C)/(5AVA)x(MA)1-xPbI3

Screen printing

Spray coating Pressure FTO/c-TiO2/mp-TiO2/MAPbI3/spiroprocessing MeOTAD/Au method FTO/SnO2/(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3/sp Solvent-bath iro-MeOTAD/Au process FTO/c-TiO2/MAPbI3-xClx/PTAA/Au

Microquanta Semiconductor Co., Ltd.

---

Solaronix SA FTO/SnO2/C60/Cs0.1FA0.9PbI3/spiroMeOTAD/Au FTO/SnO2/CsxFA1-xPbI3-yBry/spiroMeOTAD/Au FTO/TiO2/Cs0.07FA0.93PbI3/spiroMeOTAD/Au FTO/TiO2/FAPb(I0.85Br0.15)3/spiroMeOTAD/Au FTO/TiO2/FAPbI3/spiro-MeOTAD/Au

Printing

FTO/c-TiO2/mp-TiO2/MAPbI3−xClx/spiroMeOTAD/Au

CH3NH2-gas treatment

HCVD

4

6´46.2

17

6.5´30

16

6.5´55

90 (6´15)

14.1 (13.3b) 15 (15.3b) 15 (14.6b)

~20.8

4.4

~61.5

19.5

~18.2

72.1

20.3

~17.1

68.9

28

27

40

100 (10´10)

5

---

0.93

1.35

2.75

25

36

17.6

25 (5´5)

8

---

10.6

3.25

6.14

53

49

25

---

11.1

17.3

21.2

67.9

23

4.75´130

11.8

19

20.8

70.6

44

---

11.7CE

14.36

1.073/ cellCE

75.8 68.0

151.9 142

168.8 (12.5´13.5) 149.5 (11.5´13)

703da (24.15 ´29.1)

---

802da ITO/Cu-oxide/MAPbI2.7Br0.3/PCBM/BCP/Ag

Page 18 of 68

33

---

22

---

11.6CE

15.83

1.081/ cellCE

4, 8, 12

25 (26.7ap ) 31 70

---

4

---

15

~4.4

~4.5

75

50

50 (5´10) 100 (10´10)

4 10

7.8´99.4 7´100

10.5 10.7

19.6 17.7

3.72 9.6

57.5 62.9

39

49

100 (10´10)

10

5.3´93

10.4

2

9.3

56

48

46.7

100 (10´10)

8

7´85

11.2

2.2

7.1

70.4

47

198 (435.6ap)

623.7 (21´29.7) A4-size

22

5´180

3.2

0.5

18.2

38.9

38

40

100 (10´10)

10

~4´100

15.5

2.1

10.5

70.2

41

36.1ap

64 (8´8)

10

---

15.7 (12.1CE)

2 (2CE)

53.6ap

100 (10´10)

12

---

13.9

1.7

17.277

---

7

---

500

24

---

100 (10´10)

14

da

--82.6 (91.8da)

17.25

CE

20.66

10.5 75.7 (8.36CE) (71.5CE) 13.4

CE

12 --10.37 1.42 6.7´98 (9.34 da) (1.28da)

1.07

CE

62 78.1

43 131

CE

8

---

---

132

13.55

59.6

114

CVD

41.25

64 (8´8)

---

---

12.24

2.25

9.18

52.8

117

HCVD

12

25 (5´5)

6

4.1´49

14.6

3.67

5.84

0.681

119

HCVD

12

25 (5´5)

6

4.1´49

14.7

3.55

6.29

0.66

118

HCVD

12 15.4

25 (5´5) 25 (5´5)

6 6

4.1´49 5.2´49

9.0 5.8

2.97 2.53

5.64 4.62

0.54 0.49

100

12

25 (5´5)

6

4.1´49

15.3

3.66

6.65

63

113

326

Abbreviations: ITO = indium tin oxide; FTO = fluorine doped tin oxide; c-TiO2 = compact TiO2;

327

mp = mesoporous TiO2; spiro-MeOTAD = 2,2’,7,7’-tetrakis-(N,N-di-4-methoxyphenylamino)-

328

9,9’-spirobifluorene; PCBM = [6,6]-phenyl-C60,61 butyric acid methyl ester; PTAA = Poly[bis(4-

329

phenyl)(2,4,6-trimethylphenyl)amine];

330

ethylenedioxythiophene):poly(styrenesulfonate);

PEDOT:PSS P3HT

=

=

poly(3,4-

Poly(3-hexylthiophene-2,5-diyl)


Page 19 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

331

regioregular; PC71BM = [6,6]-Phenyl C71 butyric acid methyl ester; BCP = bathocuproine; 5-

332

AVA = 5-aminovaleric acid.

333

In order to obtain larger area and high quality perovskite films, Liu, Li and coworkers developed

334

a technology of alternating vacuum deposition (AVP) in 2015,98 as shown in Figure 3a. The

335

perovskite film was deposited using a layer-by-layer method. The PbCl2 was first evaporated onto

336

the substrate in a vacuum system, and then the CH3NH3I was thermally sublimed onto the PbCl2

337

film. They then repeated the process until sufficient coating thickness is generated. Finally, the

338

perovskite film was obtained after the sample was annealed at 120 ℃ for 2 hours. The merit of the

339

AVP technology is that the more volatile organic component does not interfere with the high

340

temperature evaporation of the inorganic moiety and therefore both of them can be well-controlled

341

separately. The PCE of large area (1 cm2) perovskite solar cells reached 13.84%, one of the highest

342

values at that time for the large area perovskite devices.98 Another process is to fabricate the

343

perovskite solar cells using direct contact deposition,99, 133 as shown in Figure 3b. This approach

344

combines the advantages of the short reaction time, facile fabrication, exceptional uniformity, good

345

reproducibility, high device performance and up-scalability, leading to uniform deposition over

346

large area.


ACS Energy Letters

Current Density (mA/cm2)

a Alternated deposition

b FTO/c-TiO2 FTO/c-TiO2 PbI2

15 min

CH3NH3PbI3

CH3NH3I powder

CH3NH3I powder

Heating (150 oC)

Heating (150 oC)

Current Density (mA/cm2)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 68

20 16

1 cm2

12

PCE: 13.84%

8 4 0

0.0

0.2

0.4 0.6 Voltage (V)

0.8

1.0

20 15 10 5

! = 12.6% Area: 1 cm2

0 0.0

347

0.2

0.4 0.6 Voltage (V)

0.8

1.0

348

Figure 3. Illustrate the fabrication of perovskite films and the performance for large area

349

perovskite devices by (a) Alternating vacuum deposition (Reproduced by permission of The Royal

350

Society of Chemistry)98 and (b) Direct contact deposition (reprinted with permission from ref. 133.

351

Copyright 2015 Elsevier).

352

Solar module architecture considerations. Another issue that need to be considered during the

353

fabrication of perovskite solar modules is the relatively inherent high resistance of transparent

354

conducting electrode, e.g., fluorine-doped tin oxide (FTO) and indium-doped tin oxide (ITO).134

355

To solve this issue, the solar cell/module architecture design is of vital importance. There are

356

basically two architectures for thin film solar module fabrication, i.e., series connection and

357

parallel connection (Figure 2), both of which are designed to lower the impact of TCO resistance

358

and to meet the voltage and current requirements for desired applications.67, 135 A single-junction

359

solar cell is often inadequate on the basis of reported maximum power point (MPP) voltage and

360

current (VMPP, IMPP), which scales with the band gap and crystal quality of PV material;136 for


Page 21 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

361

example, VMPP of a typical single-crystalline silicon solar cell is 0.66 V, while GaAs is around

362

1.02 V, and GaInP has the highest VMPP of 1.36 V; polycrystalline films such as CIGS and MAPbI3

363

perovskite generate VMPP of 0.63 V and 0.9 V, respectively, corresponding to the champion

364

laboratory cells and submodules.8

365 366

When the individual cells are connected to form series or parallel architecture as shown in Figure

367

2, the inter-connection area usually does not generate photocurrent and hence it is called dead area.

368

The ratio of the active area to the total substrate area is defined as the geometric fill factor (GFF)

369

of the solar module. To make better use of the light, the dead area should be kept as small as

370

possible. However, there are other requirements when designing the inter-connection structures in

371

both series and parallel architectures. It is not possible to simply increase the size of the electrode

372

area because it leads to the increased series resistance when collecting photo-generated charge

373

carriers. As a consequence, this higher series resistance leads to energy losses in solar cells

374

visualized by a lower FF in the photocurrent density-voltage (J-V) curves.134 The shape of the

375

electrodes also affects the energy output even keeping the electrode area the same.137-138 Often

376

each individual solar cell is in the shape of square, rectangular and strip. As the aspect ratio

377

decreases (i.e., reducing electrode width), the average series resistance is lower and solar cells

378

show higher FF and PCE.138 On the basis of above considerations, a strip shaped electrode for each

379

individual cell can output higher energy with less energy loss for both series and parallel

380

architectures.

381 382

For series connection, the consideration is that the following inter-connection of each individual

383

cell can multiply the energy output (from voltage output) with little increase of resistance in the



Page 22 of 68

384

inter-connection area (Figure 2). The inter-connection area is formed by three patterning lines

385

often designated as P1, P2 and P3.127 P1 and P3 are used to separate the bottom and top electrodes

386

of each individual cell, respectively. P2 is to form the inter-connection between the top electrode

387

of one cell and the bottom electrode of the next adjacent cell in the series connection architecture.

388

Note that the inter-connection area is a dead area that will also be included in the calculations of

389

total-area performance. GFF can be defined based on the cross-sectional view as the ratio between

390

the active area and the total area that includes the dead area used for interconnection.134 A balance

391

is needed between the maximal usage of the module area to absorb light and minimization of the

392

effect of series resistance.

393 394

For the series connection architecture, normally the dead area is limited by the patterning

395

technique, which is mainly based on laser or mechanical scribing processes. Without taking into

396

account the contact resistance of a fixed dead area width of 280 µm, Galagan and coworkers

397

calculated the relation between the module efficiency and the width of active area for each

398

individual cell on TCO substrates with different sheet resistance.134 It was shown that by

399

employing TCOs with lower sheet resistance, one could enlarge the width of each individual cell

400

active area and thereby enable a higher GFF to reach a higher efficiency. A stripe width in the

401

range of 3-7 mm is beneficial for attaining high PCEs on TCO substrates with 10 Ohm/square

402

sheet resistance. Realistically, to make sure that the inter-connection area does not lead to

403

additional increase in series resistance, the inter-connection area (P2) should be wide enough and

404

it depends on the contact resistance between the top electrode of one cell and the bottom electrode

405

of the next cell. For example, the compact (c)-TiO2 layer (one of the most used electron transport

406

layer (ETL)) deposited by spray pyrolysis deposition adheres tightly to the underlying FTO, which


Page 23 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

407

makes it difficult to remove.139 In comparison with FTO/c-TiO2/Au, FTO/Au has a lower contact

408

resistance. The contact resistance can be characterized by the transfer length measurement

409

technique.139 One way to reduce the contact resistance caused by c-TiO2 is to decrease the

410

thickness of c-TiO2. The decrease of c-TiO2 thickness in the inter-connection area will also

411

decrease the c-TiO2 thickness in the active area due to the uniform coating. In this case, the optimal

412

thickness of c-TiO2 for a small area cell and large area module can be substantially different as

413

reported by Li, Zhu and coworkers.140 To overcome this issue, Qi and coworkers used a high

414

mobility SnO2 thin film as electron transport layer to help lower the contact resistance in the

415

perovskite solar module fabrication.127

416 417

The parallel architecture forms low sheet resistance TCO by metal finger structure on TCO.141

418

This is an important way to make a large area single cell with large photocurrent output that can

419

match a silicon solar cell to form a two-terminal tandem structure.142 However, the area coated

420

with the metal finger electrode is also a dead area that light cannot pass through (Figure 2). A

421

larger dead area leads to a lower sheet resistance and thus a higher fill factor. However, the current

422

density is lower. In addition, the design and shape of the finger electrode affect the sheet resistance.

423

Ho-Baillie and coworkers. studied systematically the influences of different structures and designs

424

of the finger electrodes on the solar cell performance.135 A certified efficiency of 12.1% on a

425

designated area of 16 cm2 has been reported by incorporating a metal finger design.143

426 427

Upscalable HTLs and ETLs. The majority of large area device architectures that lead to high

428

performance

429

methoxyphenylamine)-9,9ʹ-spirobifluorene (spiro-MeOTAD) as HTL (Table 1). Only a few works

430

showed that solution-processed spiro-MeOTAD is also compatible with large area coating

solar

modules

employ

spin-coated

2,2ʹ,7,7ʹ-tetrakis(N,N-di-p-



Page 24 of 68

431

techniques such as slot-die coating.33, 144 However, in addition to solvent toxicity,145 long-term

432

stability issues were previously reported57, 146-149 when employing spiro-MeOTAD as HTLs due to

433

for example film crystallization,150 the strong influence of air exposure on conductivity and

434

interfacial energy level variations,151-153 photo-oxidation of spiro-MeOTAD,154 morphological

435

deformation at high temperature (80 ˚C and above) leading to formation of large voids in the spiro-

436

MeOTAD film,155-156 diffusion of Au or other metal electrode materials into spiro-MeOTAD

437

layer,157-158 and iodization of top electrode due to high temperature.158 Alternatively, ~25 cm2 and

438

49 cm2 poly(3-hexyl-thiophene (P3HT) film by bar coating,129 100 cm2 P3HT film by doctor

439

blading,31 and 90 cm2 poly(bis(4-phenyl) (2,4,6-trimethylphenyl) amine) (PTAA) by doctor

440

balding27 are a few examples demonstrating other promising HTLs in solar module applications.

441

Furthermore, employment of vapor-based techniques in large area HTL coating is a suitable way

442

for the fabrication of perovskite solar modules avoiding the complication of toxic solvents and

443

enabling uniform, smooth, and pinhole free HTL layers, which have been demonstrated only in

444

small area perovskite solar cells.57, 93, 116, 159-161

445 446

Large area ETL coatings are mainly based on metal oxides and fullerene and its derivates (Table

447

1), which are compatible with upscaling techniques of spraying coating,129 slot-die coating,130

448

thermal evaporation27 and sputtering.127, 162 Although spray coating of compact TiO2 ETL is widely

449

used, it requires high temperature pyrolysis and has a high resistance retarding charge transfer in

450

a solar module structure.17 Considering the fabrication costs and interconnection quality of solar

451

modules, some other low temperature processes have been developed, such as room temperature

452

sputtered TiO2162 which are also compatible for flexible perovskite solar modules.121 Among these

453

alternatives, SnO2 attracts particular attention for solar cell and module fabrication. For example,


Page 25 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

454

the commercially available SnO2 solution can be uniformly coated by slot-die coating and the

455

resulted flexible solar module exhibits promising efficiency.130 Furthermore, SnO2 can be sputter

456

deposited at room temperature without any thermal annealing.127 Due to high conductivity and low

457

film thickness, the coated SnO2 layer does not decrease the interconnection quality in a solar

458

module. A large solar module with 22.8 cm2 designated area and sputtered SnO2 shows an

459

efficiency over 12%.127 Recently a spin coated self-assembled SnO2 layer has been applied for

460

modules with an area of 100 cm2, which exhibits an efficiency up to 14%.128 Thermal evaporation

461

of C60 and BCP has been applied in inverted structured solar modules, which exhibit an efficiency

462

of 14.6% with an area of 57 cm2.27 The metal oxide ETL is also cheap. Considering the cost aspects

463

and stability, the commonly employed organic HTLs such as spiro-MeOTAD and PTAA are

464

expected to be replaced with some other low-cost inorganic materials (Table 2).

465 466

Carbon electrodes. Although it is only about one decade since PSC research was introduced,

467

there have been tremendous amount of efforts worldwide contributed to the rapid rise in PCEs.

468

Keeping at the current research pace, there may be a brighter future for the PSC technology to

469

compete for a portion in the annual market share of hundreds of billion-dollar worth of PV

470

technology. To make this goal achievable, low-cost, long term stability, simpler fabrication

471

protocols, and field testing profiles of perovskite solar modules will play a vital role. In PSCs,

472

organic materials such as poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS),

473

2,2’,7,7’-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9’-spirobifluorene

474

spiro-OMeTAD), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), and poly(3-hexyl-

475

thiophene (P3HT) are usually applied as hole transport layers (HTLs); gold and silver are used as

476

electrode materials in order to achieve high performances.43, 55, 96, 129, 163 However, organic HTLs

(spiro-MeOTAD

or



Page 26 of 68

477

and Au metal as electrode constitute a major portion of the fabrication cost of perovskite solar

478

modules, i.e., about 64% of the total raw material cost as summarized in Table 2 and Figure 2. The

479

cost of HTLs corresponds to 49% of the total module cost, and Au metal as electrode represents

480

15% of the total module cost. Besides high cost, perovskite solar modules that employ organic

481

HTL/Au (or Ag) exhibited unstable performance because organic HTLs are susceptible to

482

migration of metal ions from metal electrode and halide ions from perovskite.152, 164-165 Therefore,

483

after the reports showing that perovskites could serve as not only light harvester materials but also

484

as effective hole conductor,166-167 the development of organic HTL-free PSCs became an active

485

research topic in facilitating upscaling as well as addressing stability issues.168-171 In particular,

486

carbon is the most suitable electrode material among the few explored hole selective electrodes in

487

organic HTL-free PSCs (such as gold and nickel).166, 172 Carbon electrode has the advantages of

488

being earth abundant, cheap, chemically inert, instinct hydrophobic, highly conductive and flexible,

489

and also exhibiting a high device stability when employed in PSCs. At present the most stable

490

PSCs are fabricated using carbon as electrode without HTL, demonstrating almost zero loss in

491

performance when operated for more than 10,000 hours at 55 oC.47

492 493

In the context of lab-scale small area devices, the performance of carbon-based PSCs (C-PSCs)

494

is still significantly lower than the conventional PSCs based on metal electrode and organic HTL.

495

Interestingly, when upscaling is considered, there is a smaller efficiency gap between carbon based

496

solar modules and metal electrode/HTL based modules as summarized in Table 1 and Figure 1.

497

To date, the PCE of small area HTL-free C-PSCs has increased from 6.64% to 16.37% in seven

498

years.167, 170 One reason that relates to the lower performance of HTL-free C-PSCs is the limited

499

hole selectivity of carbon materials. The certified highest PCE of carbon-based PSCs is 17.8%.173


Page 27 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

500

However, this C-PSC employed P3HT/graphene composite as HTL to enhanced the performance.

501

Researchers have conducted studies to replace expensive spiro-MeOTAD HTL with low-cost

502

inorganic p-type semiconductors, such as copper(I) thiocyanate (CuSCN)174-176, CuI177, NiO178, or

503

low-cost small molecule p-type semiconductors copper phthalocyanine (CuPc)179. The resultant

504

devices showed higher stability compared with the devices using organic HTL.180 Replaced with

505

CuPc HTL, the C-PSCs achieved 17.78% PCE.181 Another factor causing the lower performance

506

of C-PSCs is the poor interface morphology between carbon electrode and perovskite. As carbon

507

electrodes are generally constituted by graphite182-184, carbon black169, 185, carbon nanotubes,170, 186-

508

188

509

interface. Based on the interface structure, there are two main structures for C-PSCs, including a

510

bi-interface

511

TiO2/perovskite/carbon) and a triple interface structure (such as FTO/c-TiO2/(mp-TiO2/mp-

512

ZrO2/mp-carbon)/perovskite). Interface engineering plays a crucial role in the improvement of the

513

C-PSCs performance.189 For bi-interfacial structure PSCs, a dense perovskite film is needed, and

514

it is necessary to enhance the interfacial contact between carbon and perovskite. For triple

515

interfacial structure PSCs, it is necessary to optimize perovskite precursors and mesoporous-

516

structure for easy infiltration of perovskite solution.

their morphologies are usually rough, which affects the contact at the perovskite/carbon

structure

(such

as

FTO/c-TiO2/with

or

without

mesoporous

(mp)-

517 518

The large gap between C-PSCs and conventional PSCs may not be limited only by the inherent

519

property of C-PSCs but also as a consequence of lack of optimization. For example, for

520

conventional PSCs, gold or silver are widely employed as electrode and their properties such as

521

Femi level, conductivity, and reflection have been systematically studied. It is important to

522

gradually accumulate knowledge based on device working principles and device optimization.



Page 28 of 68

523

However, most of the reports employed commercial carbon paste purchased directly from

524

commercial market. As a consequence, it is difficult to know a priori the specific chemical

525

composition because such information is often non-disclosable. The companies supplying high-

526

quality carbon pastes include Guangzhou Seaside Technology Co., Ltd,190-191 Shanghai MaterWin

527

New Materials Co., Ltd,192-194 Shenzhen DongDaLai Co., Ltd, China40, 181, 195-196. These carbon

528

pastes are often mixed with various components and in different ratios, which very likely are the

529

key reasons responsible for their vastly different physico-chemical properties. For example,

530

different carbon paste products likely show work function variations, which can lead to energy

531

level alignment difference with the perovskite layer and therefore resulting in different overall

532

device performance. Secondly, the commonly used carbon paste is constituted of carbon black,

533

graphite, and still lacks effective hole selectivity especially for HTL-free C-PSCs. To solve this

534

problem effectively, it is vital to have in-house development of new carbon electrodes with

535

superior stability and electrical properties as well as with proper energy level alignments according

536

to the perovskite of choice.

537 538

Although C-PSCs is promising to achieve large-scale production for commercialization, few

539

reported works successfully fabricated the large-scale and efficient C-PSCs modules.38-39, 47-48

540

Among the carbon electrode deposition methods, including doctor-blade,191,

541

printing,169 drop-casting187 and screen printing method,199 the screen printing shows the best

542

possibility in making large modules. In the past three years, by using screen printing, large C-PSCs

543

modules are successfully fabricated with the upscalable size from the beginning 10´10 cm2 with

544

the active area of 47.6 cm2,47 to the A4 size substrate with the active area of 198 cm2.38 All these

196-198

inkjet


Page 29 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

545

C-PSCs are based on the architecture of a triple interface structure with the PCE ranging from 3%

546

to 11%.

547 548

Table 2. Cost of raw materials in fabricating a perovskite solar panel with a total area of 1 m2 and

549

a GFF of 90%. Usage200

Price (USD)

Sub-total Cost (USD)

Total cost per designated item (USD)

FTO glass

1.00 m2

228.20

228.20

229.06

Deionized water

33.00 ml

0.012/L201

< 0.01

Isopropanol1

33.00 ml

0.013/ml

0.43

33.00 ml

0.013/ml

0.43

TAA

19.20 ml

0.18/ml

3.46

Ethanol

33.00 ml

0.056/ml

1.85

Deionized water

33.00 ml

0.012/L

0.001

TiO2 ink

4.94 g

2.90/g

14.33

14.33

PbI2

1.38 g

0.20/g

0.28

1.34

CH3NH3I

0.14 g

2.70/g

0.38

Isopropanol2

14.30 ml

0.043/ml

0.62

DMF

3.00 ml

0.019/ml

0.06

Spiro-MeOTAD

0.85 g

478.10/g

406.38

Chlorobenzene

10.70 ml

0.027/ml

0.29

1.65 g

76.93/g

126.93

Raw material

Substrate patterning

1

Acetone

Blocking layer 5.31

Perovskite layer

HTL 406.67

Cathode Au

126.93

Encapsulation



UV Resin XNR5516Z

3.20 g

Three bond 3035B

3.20 g 200

Page 30 of 68

10.00/g

32.00

6.13/g

19.62

550

Usage data are collected from ref.

551

information with the exchange rate 1 JPY=0.0091 USD, besides the price of deionized water from

552

ref.

553

Chlorobenzene (99.0 %, 500 ml), Acetone (Guaranteed Reagent, 3 L), Isopropanol2 (super

554

dehydrated, 3 L), DMF (super dehydrated, 3 L) and ethanol (super dehydrated, 3L) from Wako

555

(https://labchem-wako.fujifilm.com); TAA (75 wt. % in isopropanol, 500 ml) from Sigma Aldrich

556

(http://sigmaaldrich.com); MAI (100 g) and TiO2 ink (1 kg) from Greatcell Solar Ltd

557

(http://www.greatcellsolar.com); Spiro-MeOTAD (1 g) from Merck.

201

. The price information is collected according to our lab

. Specifically, FTO from PV-tech Co., Ltd.; Isopropanol1 (Guaranteed Reagent, 3 L),

558

Summary and Outlook. This year marks one decade of PSC research. We have witnessed

559

outstanding achievements including fundamental science and technologically-related strategies

560

(Figure 4).52 A key question remains, i.e., what does perovskite PV technology need the most for

561

developing efficient and stable perovskite-based solar modules?202 In this perspective, we discuss

562

the progress of solution- and vapor-based methods that have been demonstrated with some initial

563

success in upscalable fabrication of perovskite solar modules with total areas larger than 10 cm2

564

(Figures 1 and 4).203 From Figure 1 we can obtain some insights, e.g., which solar parameter is the

565

major bottleneck for the overall solar module performance when compared with small PSCs. First,

566

there is a large gap in PCE when comparing the PCE values of small area cells and large area

567

modules. While the Voc and FF plots show the small gaps between small area cells and large area

568

modules, a major gap occurs in the Jsc plot. To quantify the Jsc gap between small area perovskite

569

solar cells and perovskite solar modules, we calculate the difference value in percentage between

570

the averaged Jsc value based on all the reported modules (𝐽#$

&'()*+

= 18.14 mA/cm2) and the


Page 31 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

,-.,+/0

= 25.2 mA/cm2) in Figure 1 (dashed line). The calculated JSC gap corresponds

571

highest Jsc (𝐽#$

572

to 1 − 𝐽#$

573

are substantially smaller compared to the Jsc gap (28%).

&'()*+

,-.,+/0

/ 𝐽#$

= 0.28 (or 28%). As a comparison, the Voc gap (19%) and FF gap (21%)

574 575

In a series interconnected module, Isc of the module is determined by the smallest Isc among

576

the cells; the overall Isc of the module will be dominated by the lowest Isc among the cells (Isc =

577

Jsc ´ area). Ideally, variations in Jsc are not expected to be observed if the coated layers within the

578

solar modules are uniform and the scribing patterns are well-delineated. Defective scribes (P1, P3)

579

may produce cells with undefined active areas due to slight shift or tilting of the patterning lines,

580

which compromises Jsc. In addition to P1, P2, and P3 patterning as discussed, electrical isolation

581

and encapsulation of a module requires the removal of the full structure of the front contact,

582

absorber layer, and back contact at the edges of a solar module (boarder isolation or edge isolation,

583

P4).204 If P4 is defective in some regions, it also affects the effective cell area.

584 585

The FF reduction is mostly caused by the increased Rs, which is mainly dominated by high sheet

586

resistance of TCO and the quality of interconnects. The strategies to reduce the TCO resistance

587

are summarized as follows: (i) by increasing the thickness of the TCO to reduce sheet resistance.

588

However, in this way the transmittance will be also be reduced and a balance should be

589

considered.138 (ii) The development of better TCO with nanomaterials that shows both low sheet

590

resistance and high transmittance.205 In parallel, improvements in the quality of interconnects by

591

engineering measures need be considered for enhancing FF, such as134 (iii) widening P2 to cover

592

the entire area between P1 and P3, but still maintaining the shorter width between the individual

593

cells, and (iv) optimizing interconnecting methods such as laser or mechanical scribing.



Page 32 of 68

594 595

In a series connection, the total Voc is the sum of each individual cell. In Figure 1c, we can see

596

the evaluation of the average Voc for each individual cell as a function of module area. The reduced

597

Voc for each individual cell cause the gap between small area cell and large area module.

598

Considering each individual cell, a large area cell can be considered as many smaller area sub-

599

cells connected in parallel, Voc of the large area cell essentially takes the smallest value. Thus, the

600

reduction of Voc may be induced by reduced shunt resistance caused by several factors such as (i)

601

pinholes, (ii) particulates, (iii) interconnects (P1 and P3 are not clean/resistive enough; the P3

602

process damages the surrounding perovskite causing leakage), (iv) non-uniformity (if a particular

603

area in a particular layer is too thin); (v) lack of proper edge isolation patterning (P4).

604 605

Because PCE is proportional to the products of Jsc, Voc, and FF, all of these gap losses

606

contribute with an equal weight to the large gap in the solar module PCE (53%). The main losses

607

in the solar module efficiencies are related to the challenges in fabricating high quality perovskite

608

films and optimization of module design, which includes the balance between each of individual

609

active cells width and dead area width. Fortunately, the scribing related problems are mostly

610

engineering issues. Once it gets into large area production, these problems can be solved by

611

engineering measures.


Page 33 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

612 613

Figure 4. (a) Selected lab-scale perovskite-based solar cell efficiencies and (b) comparison with

614

large area perovskite solar modules grouped according to the coating methods.146, 148, 206 The

615

related reported data are 3.8%,207 6.5%,111 9.7%,208 14.14%,55 16.15%,109 17.91%,163 20.11%,209

616

21.1%,110 22.13%,210 22.67%,129 23.32%,15 23.7%5 and 24.2%.5 Developments of lab scale PSCs

617

can be roughly divided into three stages distinguished by the different zone colors: liquid

618

electrolyte (blue; stage 1), composition optimization (orange; stage 2), and interface engineering

619

(green; stage 3). Feasibility in applying the composition optimization strategies (Stage 2) for the

620

fabrication of large area perovskite solar modules employing upscalable methods is demonstrated

621

in Table 1. Currently the perovskite solar module research is at Stage 2. Selected best efficiencies

622

for perovskite solar modules employing different upscalable coating methods have been marked

623

with arrows. Toshiba Corporation holds the certified efficiency with the largest perovskite solar

624

module.12

625

A large number of strategies have been developed for enhancing the performance and long-term

626

operational stability in lab-scale small area PSCs. Considering the device architectures for each of

627

the corresponding PCEs displayed in Figure 4a, three stages of developments for lab-scale PSCs



Page 34 of 68

628

can be inferred. Stage 1 corresponds to the initial device architecture of liquid electrolyte

629

employing MAPbI3 and MAPbBr3 as sensitizers leading to PCEs of 3.8%,207 6.5%,111 (blue zone).

630

Stage 2 is characterized by the replacement of liquid electrolyte to all solid state spiro-MeOTAD

631

HTL in conjunction with perovskite composition optimization/engineering (orange zone) leading

632

to PCEs of 9.7%,208 14.1%,55 16.15%,109 17.91%,163 20.11%,209 21.02%,211 21.1%,110 22.13%210.

633

The strategies developed in Stage 2 helped several labs worldwide to achieve PCEs more than

634

15%. Interface engineering characterizes Stage 3 (green zone) showing the efficacy to boost up

635

further the efficiencies of PSCs leading to certified PCE values of 22.67%,129 23.32%15. The details

636

of the device architectures for the last two points of 23.7% and 24.2% in Figure 3 are still not

637

available.

638 639

The analyses of strategies that led to the best lab-scale research-cell efficiencies provide

640

important insights and promising trend that enhanced performance and stability can be achieved

641

in large area perovskite solar modules. Next, we discuss selected strategies developed in the lab-

642

scale small-area PSC research that warrant further investigation and transferring to large-area

643

perovskite solar module research. The first strategy is the perovskite composition/engineering that

644

leads to enhanced chemical stability and light absorbance.206, 212-214 12 out 40 studies surveyed in

645

this work (Table 1) employed MAPbI3 as the absorber layer. Although a consensus has not been

646

reached for this topic, and there are different opinions, a number of works have reported that it is

647

unlikely for MAPbI3-based solar cells to reach sufficient long-term stability.148, 206, 215-233 Except

648

for the first certified efficiency record (PCE=14.1% in 2012) that used pure phase MAPbI3, the

649

works to achieve the subsequent efficiency records employed perovskite materials with mixed-

650

cations (CH3NH3+, NH2CH = NH2+, Cs+) and mixed-halides (I–, Br–, Cl–).206 In the work by Saliba,


Page 35 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

651

Gratzel and coworkers,115 perovskite devices with mixed-cations and anions (e.g., FTO/c-TiO2/Li-

652

doped

653

stability and maintained ~95% of their initial performance when tested at elevated temperature of

654

85 oC in N2 environment for 500 h and under full AM 1.5 Sun-equivalent white LED lamp

655

illumination and maximum power point tracking. Similarly, Holman, McGehee and coworkers234

656

reported that FA0.83Cs0.17Pb(I0.83Br0.17)3 based PSCs packed with top glass sheet employing

657

ethylene-vinyl acetate (EVA, an elastomeric polymer binder) and butyl rubber as edge sealant can

658

withstand a 1,000 h damp heat test at 85 oC and 85% relative humidity. These and other several

659

works demonstrate that the strategy of mixed-cations and anions is effective to improve long-term

660

thermal stability.114, 119, 163, 191, 206, 235-236 On the basis of Table 1, the feasibility of preparing mixed

661

cations and anions perovskites employing upscalable techniques was demonstrated.114 The

662

stability of perovskite solar modules is another important aspect when considering upscaling.

663

Storage and operational stability data for small-area perovskite solar cells have been summarized

664

in a recent review article.57 Although stability measurements should be a standard test for

665

perovskite solar modules, currently there are only a few published results reporting perovskite

666

solar modules with both high efficiency and high stability. Upon upscaling, the stability of

667

perovskite solar modules might decrease compared with small-area perovskite solar cells. The

668

lower stability for perovskite solar modules might be caused by the high output current and voltage,

669

or the interconnection quality, which need further investigation.237 Similar to small-area perovskite

670

solar cells, there is burn-in loss at the initial stage under operation, for both solution-based and

671

HCVD-based perovskite solar modules.114, 127 Perovskite solar modules based on carbon electrode

672

show promising stability under continuous light illumination, due to the hydrophobic properties of

673

the carbon electrode.47 Encapsulation has a vital impact on the device stability, e.g., it can help

mp-TiO2/Rb0.05((Cs0.05(MA0.17FA0.83)0.95)0.95Pb(I0.83Br0.17)3/PTAA/Au)

showed

high-



Page 36 of 68

674

prevent the contact with moisture and oxygen and better withstand thermal stress.114, 238 More

675

information about encapsulation of solar modules can be found from the related review articles on

676

the encapsulation of small-area cells.239 Besides stability improvement, encapsulation can enhance

677

the mechanical strength of module and prevent the leakage of lead, which has been reported in a

678

recent study.240 Overall, encapsulation is expected to play an important role in the development of

679

large scale perovskite solar modules with high stability.241

680 681

The second strategy regards large-area deposition of ETL and HTL as well as their interfaces

682

with the perovskite layer. Large area uniform coating of these functional layers is important for

683

attaining high efficiencies. TiO2 in the form of compact and mesoporous layers has been the most

684

commonly employed low-cost metal oxide material as ETL, which has led to the majority of the

685

best certified efficiencies in solar cells and modules (Table 1).148-149 However, TiO2 is a well-

686

known photocatalytic material for H2O-splitting as well as for decomposing organic materials

687

under UV light.152, 242-243 It is desirable to minimize the negative impacts of TiO2, but still taking

688

advantage of its excellent ETL functionality. These strategies include TiO2 surface passivation for

689

reducing Ti3+ electronic trap states at the TiO2/perovskite interface,21, 243-246 use of thin insulating

690

polymer film between TiO2 and perovskite,162, 247 surface modification,248 UV filters or down-

691

conversion strategies,242, 249-251 and employing inverted device architecture.16, 20, 22, 26-27, 41, 123-124,

692

252

693

Nb2O5,260 graphene,19 PCBM,234,

694

alternatives for the TiO2 ETL and compatible with upscaling techniques. Outstanding solar cell

695

efficiencies are often achieved employing organic molecules of spiro-MeOTAD as HTL.146 As an

696

alternative, polymeric PTAA was also reported to yield high certified efficiencies.109, 146, 148, 163, 209

In addition, a number of materials such as SnO2,125-126, 131, 234, 253-258 solid-state ionic-liquid,259 244

and ZnO based ETL,36,

49, 261

have been proposed as


Page 37 of 68 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Energy Letters

697

These materials have also been commonly employed in fabricating perovskite solar modules

698

(Table 1).17-19, 28, 33, 41, 43, 121, 125-126, 131, 253 However, the prices of PTAA, spiro-MeOTAD, and Au

699

are ~2000 USD, ~500 USD, and ~80 USD per gram, respectively, which can pose cost issues when

700

upscaling.262 When one considers perovskite solar modules toward commercialization, levelized

701

cost of electricity (LCOE) and life-cycle assessment (LCA) are important parameters for

702

comparing different photovoltaic technologies.57, 200-201, 263 The raw material costs and whether

703

energy intensive operations are employed will play a major role in the evaluation of these

704

parameters (Table 2).

705 706

The third strategy is associated with defect healing in perovskites by interface engineering.

707

Defects in perovskites were previously shown to induce electronic traps within the perovskite band

708

gap, which limits efficiency, reproducibility, and lifetime. Analyzing the device structures

709

corresponding to the two points of 22.67%129, 264 and 23.32%15 in the NREL certified efficiencies

710

chart, the interface engineering and defect passivation strategies have allowed PSC to overcome

711

the barrier of 22% in efficiency (i.e., Stage 3 in Figure 4).4 In a recent work by Noh, Seo and

712

coworkers,129, 264 a material called n-hexyl trimethyl ammonium bromide (HTAB) was inserted

713

between P3HT and the perovskite layer. The interdigitation between P3HT and HTAB leads to

714

high hole-transport properties, which has the advantage over the commonly employed PTAA or

715

spiro-MeOTAD HTLs because hygroscopic dopants are not required for enhancing hole mobility

716

in this new HTL. In addition, P3HT is compatible with industrial-scale manufacturing processes.129,

717

264

718

iodide (PEAI) as a passivation material. PEAI was applied to the FA1-xMAxPbI3 (x ~ 0.08)

719

perovskite films by spin-coating. This strategy leads to the certified PCE of 23.3% in the NREL

In another work, You and coworkers15 employed organic halide salt of phenyl ethyl-ammonium



Page 38 of 68

720

chart.4 PEAI coating on the perovskite layer was proposed to heal the defects by filling the iodine

721

vacancies on the surface and at the grain boundaries.15

722 723

As the fourth strategy, the HCVD method has shown the potential in the development of

724

perovskite solar modules (Table 1, Figures 1 and 4). To further improve the long-term stability of

725

HCVD grown perovskite solar modules, it is necessary to implement corresponding methods that

726

can be readily integrated with HCVD. For instance, formation of 2D/3D hybrid perovskites is a

727

promising method in enhancing long-term operational stability.47 One of the ways to form 2D/3D

728

perovskites is via a low-pressure vapor-assisted solution process to employ PEAI doped PbI2 as

729

the precursor in the first step.253 After conversion in MAI vapor environment, the 2D/3D hybrid

730

perovskite film was formed resulting in perovskite solar cell device performance up to 19% in

731

small area devices (active area = 0.2 cm2). Other than performance and stability, fabrication cost

732

is another key metric to be analyzed in vapor-based processes. Although a slow reaction is

733

beneficial for better film control, the long reaction time in HCVD process reduces throughput, and

734

increases the energy payback time. Normally it takes 2 to 3 hours for the vapor deposition process

735

to fully convert the PbI2/PbCl2 into perovskite in a HCVD process.114, 117 Better understanding of

736

the film formation mechanism will be helpful to pin-point the necessary modifications in vapor

737

deposition processes, and more research efforts are needed in this direction. Other state-of-the-art

738

vacuum deposition processes also show respectful performance in small area devices and have

739

been summarized in a recent review article.90

740 741

Besides the four aforementioned strategies, it is equally important for us to keep in mind that we

742

also need to develop characterization techniques that are compatible with large area perovskite


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ACS Energy Letters

743

solar modules, which may provide useful feedback to these recent advances. These

744

characterization techniques need allow us to evaluate film uniformity, chemical composition

745

distribution, and identify spatially present structural defects and dust/particulates that lead to

746

shunting pathways. For example, it has been reported that false-color monochrome

747

electroluminescence mapping images and light beam induced current (LBIC) can be used to

748

characterize perovskite film quality across large areas.22,

749

characterization of the entire modules and are also compatible with in-line characterization in a

750

production factory.

118

Both techniques allow rapid

751 752

AUTHOR INFORMATION

753

* E-mail: [email protected] (Y.B.Q.)

754

*E-mail: [email protected] (S.L.)

755 756

ORCID

757

Yabing Qi: 0000-0002-4876-8049

758 759

Notes

760

The authors declare no competing financial interest.

761 762

Dr. Longbin Qiu is a postdoctoral scholar in Prof. Yabing Qi’s research unit (Energy Materials

763

and Surface Sciences Unit) at Okinawa Institute of Science and Technology Graduate University

764

in Japan. His current research focuses on the interface engineering and chemical vapor deposition

765

for scalable perovskite solar modules.

766



Page 40 of 68

767

Dr. Sisi He is a postdoctoral scholar in Prof. Yabing Qi’s research unit (Energy Materials and

768

Surface Sciences Unit) at Okinawa Institute of Science and Technology Graduate University in

769

Japan. Her research focuses on the use of carbon nanomaterials in energy and responsive devices

770

including perovskite solar cells.

771 772

Dr. Luis K. Ono is a staff scientist in Prof. Yabing Qi’s research unit (Energy Materials and Surface

773

Sciences Unit) at Okinawa Institute of Science and Technology Graduate University in Japan. His

774

current research focuses on the fundamental understanding and surface science aspects of

775

perovskite solar cells (https://groups.oist.jp/emssu).

776 777

Shengzhong Liu received his Ph.D. from Northwestern University (USA) in 1992. Following his

778

postdoctoral research at Argonne National Laboratory (Argonne, Illinois, USA), he worked for

779

various companies researching nanoscale materials, thin film solar cells, laser processing, and

780

diamond thin films. His invention of the semi-transparent photovoltaic module at BP Solar won

781

an R&D 100 award in 2002. He is now a professor at Shaanxi Normal University and Dalian

782

Institute of Chemical Physics, Chinese Academy of Sciences.

783 784

Yabing Qi is Professor and Unit Director of Energy Materials and Surface Sciences Unit at

785

Okinawa Institute of Science and Technology Graduate University in Japan. He received his B.S.,

786

M.Phil., and Ph.D. from Nanjing Univ., Hong Kong Univ. of Sci. and Tech., and UC Berkeley,

787

respectively. His research interests include perovskite solar cells, surface/interface sciences,

788

lithium

789

(https://groups.oist.jp/emssu).

ion

batteries,

organic

electronics,

energy

materials

and

devices


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ACS Energy Letters

790 791

ACKNOWLEDGMENT

792

This work was supported by funding from the Energy Materials and Surface Sciences Unit of the

793

Okinawa Institute of Science and Technology Graduate University, the OIST R&D Cluster

794

Research Program, the OIST Proof of Concept (POC) Program, and JSPS KAKENHI Grant

795

Number JP18K05266. S.L. acknowledges the funding support from the 111 Project (B14041).

796 797

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Page 68 of 68

A list of selected quotes from the manuscript:

1605 1606

Page 5, Lines 99-101: In this perspective, we analyze the current progress of solution- and

1607

vapor-based upscalable techniques that allowed fabrication of solar modules with a total area

1608

larger than 10 cm2

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Page 13, Lines 235-236: Fabrication of solar modules based on all vapor methods (i.e., solvent-

1610

free processes) could be also envisaged for the perovskite PV technology

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Page 26, Lines 477-479: Organic HTLs and Au metal as electrode constitute a major portion of

1612

the fabrication cost of perovskite solar modules, i.e., about 64% of the total raw material cost

1613

Page 33, Lines 640-642: The analyses of strategies that led to the best lab-scale research-cell

1614

efficiencies provide important insights and promising trend that enhanced performance and

1615

stability can be achieved in large area perovskite solar modules


Scalable Fabrication of Metal Halide Perovskite ... - ACS Publications

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