Green-Solvent-Processable, Dopant-Free Hole-Transporting Materials for Robust and Efficient Perovskite Solar Cells.

In addition to having proper energy levels and high hole mobility (µh) without the use of dopants, hole-transporting materials (HTMs) used in n-i-p-type perovskite solar cells (PSCs) should be processed using green solvents to enable environmentally friendly device fabrication. Although many HTMs have been assessed, due to the limited solubility of HTMs in green solvents, no green-solvent-processable HTM has been reported to date. Here, we report on a green-solvent-processable HTM, an asymmetric D-A polymer (asy-PBTBDT) that exhibits superior solubility even in the green solvent, 2-methylanisole, which is a known food additive. The new HTM is well matched with perovskites in terms of energy levels and attains a high µh (1.13 × 10-3 cm2/(V s)) even without the use of dopants. Using the HTM, we produced robust PSCs with 18.3% efficiency (91% retention after 30 days without encapsulation under 50%-75% relative humidity) without dopants; with dopants (bis(trifluoromethanesulfonyl) imide and tert-butylpyridine, a 20.0% efficiency was achieved. Therefore, it is a first report for a green-solvent-processable hole-transporting polymer, exhibiting the highest efficiencies reported so far for n-i-p devices with and without the dopants.

A Three-Step Method for the Deposition of Large Cuboids of Organic-Inorganic Perovskite and Application in Solar Cells.

A three-step method for the deposition of CH3 NH3 PbI3 perovskite films with a high crystalline structure and large cuboid overlayer morphology is reported. The method includes PbI2 deposition, which is followed by dipping into a solution of C4 H9 NH3 I (BAI) and (BA)2 PbI4 perovskite formation. In the final step, the poorly thermodynamically stable (BA)2 PbI4 phase converts into the more stable CH3 NH3 PbI3 perovskite by dipping into a solution of CH3 NH3 I. The final product is characterized by XRD, SEM, UV/Vis, and photoluminescence analysis methods. The experimental results indicate that the prepared perovskite has cuboids with high crystallinity and large sizes (up to 1 µm), as confirmed by XRD and SEM data. Photovoltaic investigations show that the three-step method results in higher solar cell efficiency (15 % enhancement in efficiency) with a better reproducibility than the conventional two-step deposition method.

Encapsulation Strategies for Highly Stable Perovskite Solar Cells under Severe Stress Testing: Damp Heat, Freezing, and Outdoor Illumination Conditions.

A key direction toward managing extrinsic instabilities in perovskite solar cells (PSCs) is encapsulation. Thus, a suitable sealing layer is required for an efficient device encapsulation, preventing moisture and oxygen ingression into the perovskite layer. In this work, a solution-based, low-cost, and commercially available bilayer structure of poly(methyl methacrylate)/styrene-butadiene (PMMA/SB) is investigated for PSCs encapsulation. Encapsulated devices retained 80% of the initial power conversion efficiency (PCE) at 85 °C temperature and 85% relative humidity after 100 h, while reference devices without SB (only PMMA) suffer from rapid and intense degradation after only 2 h, under the same condition. In addition, encapsulated devices retained 95% of the initial PCE under -15 °C freezing temperature after 6 h and retained ∼80% of the initial PCE after immersion in HCl (37%) for 90 min. Moreover, applying an additional aluminum metal sheet on the PMMA/SB protective bilayer leads to the improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.improvement of device stability up to 500 h under outdoor illumination, retaining almost 90% of the initial PCE. Considering the urge to develop reliable, scalable, and simple encapsulation for future large-area PSCs, this work establishes solution-based bilayer encapsulation, which is applicable for flexible solar modules as well as other optoelectronic devices such as light-emitting devices and photodetectors.

Optimization of CuIn1-XGaXS2 Nanoparticles and Their Application in the Hole-Transporting Layer of Highly Efficient and Stable Mixed-Halide Perovskite Solar Cells.

Inorganic hole-transport materials (HTMs) have been frequently applied in perovskite solar cells (PSCs) and are a promising solution to improve the poor stability of PSCs. In this study, we investigate solution-processed copper indium gallium disulfide (CIGS) nanocrystals (NCs) as a dopant-free inorganic HTM in n-i-p type PSCs. Moreover, Cs0.05(MA0.17-FA0.83)0.95Pb(I0.83Br0.17)3 mixed-halide perovskite with proper crystalline quality and long-time stability was utilized as the light-absorbing layer under ambient conditions. To optimize the cell performance and better charge extraction from the perovskite layer, the Ga concentration in the Cu(In1-XGaX)S2 composition was changed, and the X value was altered between 0.0 and 0.75. It was shown that the CIGS band gap enhances with increasing Ga content; thus, with tunable band gaps and engineering of the energy level alignment, a better collection of photogenerated holes and a reduced electron-hole recombination rate could be achieved. The maximum power conversion efficiency of 15.6% was obtained for the PSC with Cu(In0.5Ga0.5)S2 hole-transport layer composition, which is the highest efficiency reported so far for CIGS-based dopant-free PSCs. This value is very close to the efficiency of devices fabricated with doped spiro-OMeTAD as an organic HTM. Additionally, the stability of nonencapsulated PSCs was studied, and CIGS-based devices demonstrated 70% retention after 90 days of aging in the dark and in 50% relative humidity conditions. This result is quite better than the similar measurements for the doped spiro-OMeTAD-based devices.

Perovskite/Hole Transport Layer Interface Improvement by Solvent Engineering of Spiro-OMeTAD Precursor Solution.

Perovskite solar cells (PSCs) are one of the most promising emerging energy-conversion technologies because of their high power conversion efficiencies (PCEs) and potentially low fabrication cost. To improve PCE, it is necessary to develop PSCs with good interfacial engineering to reduce the trap states and carrier transport barriers present at the various interfaces of the PSCs' architecture. This work reports a facile method to improve the interface between the perovskite absorber layer and the hole transport layer (HTL) by adding a small amount of acetonitrile (ACN) in the Spiro-OMeTAD precursor solution. This small amount of ACN dissolves the surface of the perovskite layer, allowing the formation of an interdiffusion structure between perovskite and Spiro-OMeTAD layers. This modification allows for an improved electrical contact, enhanced collection of holes, and reduced recombination losses at the interface between the perovskite and Spiro-OMeTAD layers and, consequently, enhances the PCE. A maximum PCE of 19.7% with low hysteresis and a steady-state power conversion efficiency of 19.0% is obtained for optimized PSCs.

Gradated Mixed Hole Transport Layer in a Perovskite Solar Cell: Improving Moisture Stability and Efficiency.

We demonstrate a simple and facile way to improve the efficiency and moisture stability of perovskite solar cells using commercially available hole transport materials, 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD) and poly(3-hexylthiophene) (P3HT). The hole transport layer (HTL) composed of mixed spiro-OMeTAD and P3HT exhibited favorable vertical phase separation. The hydrophobic P3HT was more distributed near the surface (the air atmosphere), whereas the hydrophilic spiro-OMeTAD was more distributed near the perovskite layer. This vertical separation resulted in improved moisture stability by effectively blocking moisture in air. In addition, the optimized composition of spiro-OMeTAD and P3HT improved the efficiency of the solar cells by enabling fast intramolecular charge transport. In addition, a suitable energy level alignment facilitated charge transfer. A device fabricated using the mixed HTL exhibited enhanced performance, demonstrating 18.9% power conversion efficiency and improved moisture stability.

Broadband and Low-Loss Plasmonic Light Trapping in Dye-Sensitized Solar Cells Using Micrometer-Scale Rodlike and Spherical Core-Shell Plasmonic Particles.

Dielectric scattering particles have widely been used as embedded scattering elements in dye-sensitized solar cells (DSCs) to improve the optical absorption of the device. Here we systematically study rodlike and spherical core-shell silica@Ag particles as more effective alternatives to the dielectric scattering particles. The wavelength-scale silica@Ag particles with sufficiently thin Ag shell support hybrid plasmonic-photonic resonance modes that have low parasitic absorption losses and a broadband optical response. Both of these features lead to their successful deployment in light trapping in high-efficiency DSCs. Optimized rodlike silica@Ag@silica particles improve the power conversion efficiency of a DSC from 6.33 to 8.91%. The dimension, surface morphology, and concentration of these particles are optimized to achieve maximal efficiency enhancement. The rodlike silica particles are prepared in a simple one-pot synthesis process and then are coated with Ag in a liquid-phase deposition process by reducing an Ag salt. The aspect ratio of silica rods is tuned by adjusting the temperature and duration of the growth process, whereas the morphology of Ag shell is tailored by controlling the reduction rate of Ag salt, where slower reduction in a polyol process gives a smoother Ag shell. Using optical calculations, the superior performance of the plasmonic core-shell particles is related to the large number of hybrid photonic-plasmonic resonance modes that they support.