Argon Plasma Treatment to Tune Perovskite Surface Composition for

High Efficiency Solar Cells and Fast Photodetectors

The surface composition of perovskite films is very sensitive to film processing and can deviate from the

optimal, which generates unfavorable defects and results in efficiency loss in solar cells and slow

response speed in photodetectors. An argon plasma treatment is introduced to modify the surface

composition by tuning the ratio of organic and inorganic components as well as defect type before

deposition of the passivating layer. It can efficiently enhance the charge collection across the

perovskite–electrode interface by suppressing charge recombination. Therefore, perovskite solar cells

with argon plasma treatment yield enhanced efficiency to 20.4% and perovskite photodetectors can

reach their fastest respond speed, which is solely limited by the carrier mobility.

Oxygen-plasma processed Spiro-OMeTAD toward high performance for

Perovskite solar cell

Efficient perovskite solar cell was achieved using a small hole transport material, SpiroOMeTAD, after

oxygen plasma treatment. It was demonstrated that the plasma treatment of hole transport layer for

the solids state perovskite solar cell was enhanced power conversion efficiency. Reason for enhancing

the cell performance of solar cell was good match of homo energy level between Perovskite and Spiro-

OMeTAD. It leads to transfer well hole carrier at Active/HTL interface. This study obtained highly

improved performance by a current density of 25.4 mA/cm2 , an open-circuit voltage of 1.02 V, and a fill

factor of 60.2 %, which resulted showed above 15% of cell efficiency.

In conclusion, we have demonstrated not only a novel approach Spiro-OmeTAD to enhance photovoltaic

performance, but also a useful treatment system to introduce the correlation between CH3NH3PbI3 and
HTL of perovskite solar cell. Specifically, our research underlines that using oxygen plasma of HTM and

MAPbI3 well-matched hole conductors is key to enhance performance. A central finding of our study is

that HTM based on the spiroOmeTAD after 15min was obtained the highest efficiency of 15.6%, with

higher FF and Voc values than the other time. These results will induce useful and cost-effective of HTM

for solar cells industry in the future. We believe that the present findings apply existing and new HTM

for organic solar cell to achieve high-efficiency and low-cost solar cells.

Perovskite Solar Cells with Low-Cost TiO2 Mesoporous Photoanodes

Prepared by Rapid Low-Temperature (70 °C) Plasma Processing

This work introduces a novel method of low-temperature (70 °C) ambient-air plasma treatment

for the rapid fabrication of mesoporous titania/polysiloxane thin films in perovskite solar cells.

The mesoporous titania/polysiloxane nanocomposite mesoporous layers were prepared using

wet coating compatible with plasma post-treatment, leading to a significant and rapid (1 min)

removal of the organic part of the polysiloxane binder, together with its transformation into

amorphous silica. The application of a plasma processed mesoporous titania/silica photoanode

in a perovskite solar cell resulted in a power conversion efficiency of ∼12%, demonstrating for

the first time the feasibility of such a cold plasma processing approach for perovskite solar cell

manufacture.

This contribution presents a method for the fabrication of n−i−p perovskite solar cells using an

economically optimized TiO2/polysiloxane mesoporous (m-TiO2) photoanode fabricateby

solution processing an inkjet-printing-compatible process and low temperature ambient-air

diffuse plasma processing. A functional n−i−p CH3NH3PbI3−xClx perovskite solar cell achieving

an efficiency of up to ∼12% was fabricated by means of a plasma-processed m-TiO2

photoanode. Since research trends are shifting away from improving the efficiency of solar cells

and toward ensuring suitable properties for industrialization, particularly in terms of the stability of

devices and design for low-cost production processes, the method herein constitutes an important

improvement in fabrication methodology that may find commercial success in the manufacture of

flexible and printed electronics that require roll-to-roll lines. Processing of m-TiO2 by low-temperature

(70 °C) plasma is the most rapid ambient-air method reported for the manufacture of m-TiO2 in

perovskite solar cells. The competitive processes associated with flexible and printed electronics include

time-consuming (tens of minutes or longer) UV treatments, which take significantly longer times at

higher operating costs than plasma treatment. The low operational costs of RPS40 plasma arise from the

technically unique coplanar setup of metallic electrodes enclosed in robust Al2O3 ceramics. This

facilitates the generation of surface plasma of ultra-high-power density, on the order of ∼160 W/ cm3.

The volume power density is extremely high since the thickness of the plasma is low, at ∼0.2 mm. This is

among the highest reported power densities for ambient-air plasmas with homogeneous, diffuse

attributes and cold (∼70 °C) properties. Rapid plasma treatment of TiO2/polysiloxane leading to

TiO2/SiO2-like surfaces by means of RPS40 plasma is revealed to be a nontoxic, sustainable, and highly

feasible process, with potential for integration into the manufacture of low-cost devices, particularly

those for which the highest PCE is not a key parameter for commercial success.

CO2 Plasma-Treated TiO2 Film as an Effective Electron Transport

Layer for High-Performance Planar Perovskite Solar Cells

Perovskite solar cells (PSCs) have received great attention due to their excellent photovoltaic properties

especially for the comparable efficiency to silicon solar cells. The electron transport layer (ETL) is
regarded as a crucial medium in transporting electrons and blocking holes for PSCs. In this study, CO2

plasma generated by plasma-enhanced chemical vapor deposition (PECVD) was introduced to modify

the TiO2 ETL. The results indicated that CO2 plasma treated compact TiO2 layer exhibited better surface

hydrophilicity, higher conductivity, and lower bulk defect state density in comparison with the pristine

TiO2 film. The quality of the stoichiometric TiO2 structure was improved and the concentration of

oxygen-deficiencies induced defect sites was reduced significantly after CO2 plasma treated for 90 s. The

PSCs with TiO2 film treated by CO2 plasma for 90 s exhibited simultaneously the improved short-circuit

current (Jsc) and fill factor (FF). As a result, PSC based TiO2 ETL with CO2 plasma treatment affords a

power conversion efficiency (PCE) of 15.39%, outperforming that based on pristine TiO2 (13.54%). These

results indicate that the plasma treatment by PECVD method is an effective approach to modify ETL for

high performance planar PSCs.

We have introduced the CO2 plasma to modify the TiO2 films using PECVD system. The CO2 plasma

method can not only improve the quality of the stoichiometric TiO2 structure, but also reduce the

concentration of oxygen-deficiencies induced defect sites. The 90 s CO2 plasma treated TiO2 film

exhibited the better surface hydrophilicity, the higher conductivity, and the lower bulk defect state

density in comparison with the pristine TiO2 film. Compared to PSC based on pristine TiO2, the PSCs

with CO2 plasma treated TiO2 shown the higher JSC and FF due to the reduced electron recombination

and enhanced electron transport. Corresponding, the PCE was significantly enhanced from 13.54% to

15.39%. These results indicated that the plasma treatment by PECVD method is an effective approach to

modify ETL for high performance planar heterojunction PSCs.