Abstract Poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is a popular hole transport material in perovskite solar cells (PSCs). However, the devices with PEDOT:PSS exhibit large open‐circuit voltage (Voc) loss and low efficiency, which is attributed to mismatched energy level alignment and the poor interface of PEDOT:PSS and perovskite. Here, three polymer analogues to polyaniline (PANI), PANI–carbazole (P1), PANI–phenoxazine (P2), and PANI–phenothiazine (P3) are designed with different energy levels to modify the interface between PEDOT:PSS and the perovskite layer and improve the device performance. The effects of the polymers on the device performance are demonstrated by evaluating the work function adjustment, perovskite growth control, and interface modification in MAPbI3‐based PSCs. Low bandgap Sn–Pb‐based PSCs are also fabricated to confirm the effects of the polymers. Three effects are evaluated through the comparison study of PEDOT:PSS‐based organic solar cells and MAPbI3 PSCs based on the PEDOT:PSS modified by P1, P2, and P3. The order of contribution for the three effects is work function adjustment > surface modification > perovskite growth control. MAPbI3 PSCs modified with P2 exhibit a highVocof 1.13 V and a high‐power conversion efficiency of 21.06%. This work provides the fundamental understanding of the interface passivation effects for PEDOT:PSS‐based optoelectronic devices. 
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                            Characterization of PEDOT:PSS Nanofilms Printed via Electrically Assisted Direct Ink Deposition with Ultrasonic Vibrations
                        
                    
    
            Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has emerged as a promising conductive polymer for constructing efficient hole-transport layers (HTLs) in perovskite solar cells (PSCs). However, conventional fabrication methods, such as spin coating, spray coating, and slot-die coating, have resulted in PEDOT:PSS nanofilms with limited performance, characterized by a low density and non-uniform nanostructures. We introduce a novel 3D-printing approach called electrically assisted direct ink deposition with ultrasonic vibrations (EF-DID-UV) to overcome these challenges. This innovative printing method combines programmable acoustic field modulation with electrohydrodynamic spraying, providing a powerful tool for controlling the PEDOT:PSS nanofilm’s morphology precisely. The experimental findings indicate that when PEDOT:PSS nanofilms are crafted using horizontal ultrasonic vibrations, they demonstrate a uniform dispersion of PEDOT:PSS nanoparticles, setting them apart from instances involving vertical ultrasonic vibrations, both prior to and after the printing process. In particular, when horizontal ultrasonic vibrations are applied at a low amplitude (0.15 A) during printing, these nanofilms showcase exceptional wettability performance, with a contact angle of 16.24°, and impressive electrical conductivity of 2092 Ω/square. Given its ability to yield high-performance PEDOT:PSS nanofilms with precisely controlled nanostructures, this approach holds great promise for a wide range of nanotechnological applications, including the production of solar cells, wearable sensors, and actuators. 
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                            - Award ID(s):
- 2114119
- PAR ID:
- 10520570
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Molecules
- Volume:
- 28
- Issue:
- 20
- ISSN:
- 1420-3049
- Page Range / eLocation ID:
- 7109
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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