skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Strong-bonding hole-transport layers reduce ultraviolet degradation of perovskite solar cells
The light-emitting diodes (LEDs) used in indoor testing of perovskite solar cells do not expose them to the levels of ultraviolet (UV) radiation that they would receive in actual outdoor use. We report degradation mechanisms of p-i-n–structured perovskite solar cells under unfiltered sunlight and with LEDs. Weak chemical bonding between perovskites and polymer hole-transporting materials (HTMs) and transparent conducting oxides (TCOs) dominate the accelerated A-site cation migration, rather than direct degradation of HTMs. An aromatic phosphonic acid, [2-(9-ethyl-9H-carbazol-3-yl)ethyl]phosphonic acid (EtCz3EPA), enhanced bonding at the perovskite/HTM/TCO region with a phosphonic acid group bonded to TCOs and a nitrogen group interacting with lead in perovskites. A hybrid HTM of EtCz3EPA with strong hole-extraction polymers retained high efficiency and improved the UV stability of perovskite devices, and a champion perovskite minimodule—independently measured by the Perovskite PV Accelerator for Commercializing Technologies (PACT) center—retained operational efficiency of >16% after 29 weeks of outdoor testing.  more » « less
Award ID(s):
1848371
PAR ID:
10643121
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  more » ;  ;  ;  ;   « less
Publisher / Repository:
Science
Date Published:
Journal Name:
Science
Volume:
384
Issue:
6700
ISSN:
0036-8075
Page Range / eLocation ID:
1126 to 1134
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The influence of halogen substitutions (F, Cl, Br, and I) on the energy levels of the self‐assembled hole‐extracting molecule [2‐(9H‐Carbazol‐9‐yl)ethyl]phosphonic acid (2PACz), is investigated. It is found that the formation of self‐assembled monolayers (SAMs) of [2‐(3,6‐Difluoro‐9H‐carbazol‐9‐yl)ethyl]phosphonic acid (F‐2PACz), [2‐(3,6‐Dichloro‐9H‐carbazol‐9‐yl)ethyl]phosphonic acid (Cl‐2PACz), [2‐(3,6‐Dibromo‐9H‐carbazol‐9‐yl)ethyl]phosphonic acid (Br‐2PACz), and [2‐(3,6‐Diiodo‐9H‐carbazol‐9‐yl)ethyl]phosphonic acid (I‐2PACz) directly on indium tin oxide (ITO) increases its work function from 4.73 eV to 5.68, 5.77, 5.82, and 5.73 eV, respectively. Combining these ITO/SAM electrodes with the ternary bulk‐heterojunction (BHJ) system PM6:PM7‐Si:BTP‐eC9 yields organic photovoltaic (OPV) cells with power conversion efficiency (PCE) in the range of 17.7%–18.5%. OPVs featuring Cl‐2PACz SAMs yield the highest PCE of 18.5%, compared to cells with F‐2PACz (17.7%), Br‐2PACz (18.0%), or I‐2PACz (18.2%). Data analysis reveals that the enhanced performance of Cl‐2PACz‐based OPVs relates to the increased hole mobility, decreased interface resistance, reduced carrier recombination, and longer carrier lifetime. Furthermore, OPVs featuring Cl‐2PACz show enhanced stability under continuous illumination compared to ITO/PEDOT:PSS‐based cells. Remarkably, the introduction of the n‐dopant benzyl viologen into the BHJ further boosted the PCE of the ITO/Cl‐2PACz cells to a maximum value of 18.9%, a record‐breaking value for SAM‐based OPVs and on par with the best‐performing OPVs reported to date. 
    more » « less
  2. Abstract Organometal halide perovskite light emitting diodes (LEDs) have attracted a lot of attention in recent years, owing to the rapid progress in device efficiency. However, their short operational lifetime severely impedes the practical uses of these devices. The operating stability of perovskite LEDs are due to degradation due to ambient environment and degradation during operation. The former can be suppressed by encapsulation while the latter one is the intrinsic degradation due to the electrochemical stability of the perovskite materials. In addition, perovskites also suffer from ion migration which is a major degradation mechanism in perovskite LEDs. In this review, we specifically focus on the operational stability of perovskite LEDs. The review is divided into two parts: the first part contains a summary of various degradation mechanisms and some insight on the degradation behavior and the second part is the strategies how to improve the operational stability, especially the strategies to suppress ion migration. Based on the current advances in the literature, we finally present our perspectives to improve the device stability. 
    more » « less
  3. Abstract Tailoring the doping of semiconductors in heterojunction solar cells shows tremendous success in enhancing the performance of many types of inorganic solar cells, while it is found challenging in perovskite solar cells because of the difficulty in doping perovskites in a controllable way. Here, a small molecule of 4,4′,4″,4″′‐(pyrazine‐2,3,5,6‐tetrayl) tetrakis (N,N‐bis(4‐methoxyphenyl) aniline) (PT‐TPA) which can effectively p‐dope the surface of FAxMA1−xPbI3(FA: HC(NH2)2; MA: CH3NH3) perovskite films is reported. The intermolecular charge transfer property of PT‐TPA forms a stabilized resonance structure to accept electrons from perovskites. The doping effect increases perovskite dark conductivity and carrier concentration by up to 4737 times. Computation shows that electrons in the first two layers of octahedral cages in perovskites are transferred to PT‐TPA. After applying PT‐TPA into perovskite solar cells, the doping‐induced band bending in perovskite effectively facilitates hole extraction to hole transport layer and expels electrons toward cathode side, which reduces the charge recombination there. The optimized devices demonstrate an increased photovoltage from 1.12 to 1.17 V and an efficiency of 23.4% from photocurrent scanning with a stabilized efficiency of 22.9%. The findings demonstrate that molecular doping is an effective route to control the interfacial charge recombination in perovskite solar cells which is in complimentary to broadly applied defect passivation techniques. 
    more » « less
  4. null (Ed.)
    While typical perovskite solar cells (PSCs) with doped Spiro-OMeTAD as a hole transport material (HTM) have shown rapid increase in their power-conversion efficiencies (PCEs), their poor stability remains a big concern as the dopants and additives used with Spiro-OMeTAD have a strong tendency to diffuse into and degrade the perovskite active layer under normal operating conditions. Aiming to push forward the development of PSCs, many dopant-free small-molecular HTMs have been reported based on energetic considerations for charge transfer and criteria for charge transport. However, the PCEs of the state-of-the-art PSCs with dopant-free small-molecular HTMs are still inferior to those using doped Spiro-OMeTAD, and little attention has been paid to the interactions between the HTM and perovskite absorber in PSCs. Here, we report a facile design concept to functionalize HTMs so that they can passivate perovskite surface defects and enable perovskite active layers with lower density of surface trap states and more efficient charge transfer to the hole transport layer. As a consequence, perovskite solar cells with a functionalized HTM exhibit a champion PCE of 22.4%, the highest value for PSCs using dopant-free small molecular HTMs to date, and substantively improved operational stability under continuous illumination. With a T 80 of (1617 ± 7) h for encapsulated cells tested at 30 °C in air, the PSCs containing the functionalized HTM are among the most stable PSCs using dopant-free small-molecular HTMs. The effectiveness of our strategy is demonstrated in PSCs comprising both a state-of-the-art MA-free perovskite and MAPbI, a system having more surface defects, and implies the potential generality of our strategy for a broad class of perovskite systems, to further advance highly efficient and stable solar cells. 
    more » « less
  5. Abstract Organic‐inorganic hybrid perovskite solar cells are susceptible to multiple influencing factors such as moisture, oxygen, heat stress, ion migration. Given the complex practical working conditions for solar cells, a fundamental question is how different failure mechanisms collaborate and substantially accelerate the device degradation. In this study, it is found that ion migration can accelerate the reaction between oxygen and methylammonium lead iodide perovskite in light conditions. This is suggested since regions with local electric fields suffer from more severe decomposition. Here it is reported that cesium ions (Cs+) incorporated in perovskite lattice, with a moderate doping concentration (e.g. 5%), can function as stabilizers to efficiently interrupt such a synergistic effect between oxygen induced degradation and ion migration while retaining the high performance of perovskite solar cells. Both experimental and theoretical results suggest that 5% Cs+ions incorporation simultaneously suppresses the formation of reactive superoxide ions () as well as ion migration in perovskites by forming additional energy barriers. This A‐site cations engineering is also a promising strategy to circumvent the detrimental effect of oxygen molecules in FA‐based perovskites, which is important for developing high‐efficiency perovskite solar cells with enhanced stability. 
    more » « less