Trihalide Perovskite Research Articles

Photophysical Analysis of the Formation of Organic-Inorganic Trihalide Perovskite Films: Identification and Characterization of Crystal Nucleation and Growth.

In this work we demonstrate that the different processes occurring during hybrid organic–inorganic lead iodide perovskite film formation can be identified and analyzed by a combined in situ analysis of their photophysical and structural properties. Our observations indicate that this approach permits unambiguously identifying the crystal nucleation and growth regimes that lead to the final material having a cubic crystallographic phase, which stabilizes to the well-known tetragonal phase upon cooling to room temperature. Strong correlation between the dynamic and static photoemission results and the temperature-dependent X-ray diffraction data allows us to provide a description and to establish an approximate time scale for each one of the stages and their evolution. The combined characterization approach herein explored yields key information about the kinetics of the process, such as the link between the evolution of the defect density during film formation, revealed by a fluctuating photoluminescence quantum yield, and the gradual changes observed in the PbI2-related precursor structure.

Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability

Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability

Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability.

Organometal trihalide perovskites (OTPs) are emerging as very promising photovoltaic materials because the power conversion efficiency (PCE) of OTP solar cells quickly rises and now rivals with that of single crystal silicon solar cells after only five-years research. Their prospects to replace silicon photovoltaics to reduce the cost of renewable clean energy are boosted by the low-temperature solution processing as well as the very low-cost raw materials and relative insensitivity to defects. The flexibility, semitransparency, and vivid colors of perovskite solar cells are attractive for niche applications such as built-in photovoltaics and portable lightweight chargers. However, the low stability of current hybrid perovskite solar cells remains a serious issue to be solved before their broad application. Among all those factors that affect the stability of perovskite solar cells, ion migration in OTPs may be intrinsic and cannot be taken away by device encapsulation. The presence of ion migration has received broad attention after the report of photocurrent hysteresis in OTP based solar cells. As suggested by much direct and indirect experimental evidence, the ion migration is speculated to be the origin or an important contributing factor for many observed unusual phenomenon in OTP materials and devices, such as current-voltage hysteresis, switchable photovoltaic effect, giant dielectric constant, diminished transistor behavior at room temperature, photoinduced phase separation, photoinduced self-poling effect, and electrical-field driven reversible conversion between lead iodide (PbI2) and methylammonium lead triiodide (MAPbI3). Undoubtedly thorough insight into the ion-migration mechanism is highly desired for the development of OTP based devices to improve intrinsic stability in the dark and under illumination. In this Account, we critically review the recent progress in understanding the fundamental science on ion migration in OTP based solar cells. We look into both theoretical and experiment advances in answering these basic questions: Does ion migration occur and cause the photocurrent hysteresis in perovskite solar cells? What are the migrating ion species? How do ions migrate? How does ion migration impact the device efficiency and stability? How can ion migration be mitigated or eliminated? We also raise some questions that need to be understood and addressed in the future.

Critical kinetic control of non-stoichiometric intermediate phase transformation for efficient perovskite solar cells.

Organometal trihalide perovskites (OTP) have attracted significant attention as a low-cost and high-efficiency solar cell material. Due to the strong coordination between lead iodide (PbI2) and dimethyl sulfoxide (DMSO) solvent, a non-stoichiometric intermediate phase of MA2Pb3I8(DMSO)2 (MA = CH3NH3(+)) usually forms in the one-step deposition method that plays a critical role in attaining high power conversion efficiency. However, the kinetic understanding of how the non-stoichiometric intermediate phase transforms during thermal annealing is currently absent. In this work, we investigated such a phase transformation and provided a clear picture of three phase transition pathways as a function of annealing conditions. The interdiffusion of MAI and DMSO varies strongly with the annealing temperature and time, thus determining the final film composition and morphology. A surprising finding reveals that the best performing cells contain ∼18% of the non-stoichiometric intermediate phase, instead of pure phase OTP. The presence of such an intermediate phase enables smooth surface morphology and enhances the charge carrier lifetime. Our results highlight the importance of the intermediate phase growth kinetics that could lead to large-scale production of efficient solution processed perovskite solar cells.

Understanding of the formation of shallow level defects from the intrinsic defects of lead tri-halide perovskites.

Organic-inorganic hybrid perovskites have unique electronic properties in which deep level defects are rarely formed. This unique defect characteristic is the source of the long carrier diffusion length. This theoretical study shows what causes this characteristic formation of shallow level defects in lead tri-halide perovskites. Comparative studies between iodides and other halides showed that deep level defect states were generated for Cl based perovskites. Longer Pb-halide bond lengths and narrower band gaps are beneficial for preventing deep level defect states. Additionally, our study shows that the formation of shallow level defects does not change even when the lattice structures of the perovskites do not reach their equilibrium structures.

Correlation of energy disorder and open-circuit voltage in hybrid perovskite solar cells

Organometal trihalide perovskites have been demonstrated as excellent light absorbers for high-efficiency photovoltaic applications. Previous approaches to increasing the solar cell efficiency have focused on optimization of the grain morphology of perovskite thin films. Here, we show that the structural order of the electron transport layers also has a significant impact on solar cell performance. We demonstrate that the power conversion efficiency of CH3NH3PbI3 planar heterojunction photovoltaic cells increases from 17.1 to 19.4% when the energy disorder in the fullerene electron transport layer is reduced by a simple solvent annealing process. The increase in efficiency is the result of the enhancement in open-circuit voltage from 1.04 to 1.13 V without sacrificing the short-circuit current and fill factor. These results shed light on the origin of open-circuit voltage in perovskite solar cells, and provide a path to further increase their efficiency. Ongoing efforts are devoted to raising the efficiency of solar cells in converting energy from solar radiation. Now, improved structural order in the charge transport layers of perovskite solar cells is shown to increase the efficiency from 17.1% to 19.4%.

Solvent-Assisted Preparation of High-Performance Mesoporous CH₃NH₃Pbl₃ Perovskite Solar Cells.

Organometal trihalide perovskite based solar cells have attracted great attention worldwide since their power conversion efficiency (PCE) have risen to over 15% within only 3 years of development. Comparing with other types of perovskite solar cells, mesostructured perovskite solar cells based on CH₃NH₃Pbl₃ as light harvesting material have already demonstrated remarkable advance in performance and reproducibility. Here, we reported a mesoscopic TiO₂/CH₃NH₃Pbl₃ heterojunction solar cell with uniform perovskite thin film prepared via solvent-assisted solution processing method. The best performing device delivered photocurrent density of 20.11 mA cm⁻², open-circuit voltage of 1.02 V, and fill factor of 0.70, leading to a PCE of 14.41%. A small anomalous hysteresis in the J-V curves was observed, where the PCE at forward scan was measured to be 84% of the PCE at reverse scan. Based on a statistical analysis, the perovskite solar cells prepared by the reported method exhibited reproducible and high PCE, indicating its promising application in the fabrication of low-cost and high-efficiency perovskite solar cells.

Enhanced Performance with the Incorporation of Organo-metal Trihalide Perovskite in Nanostructured ZnO Solar Cell

The tremendous developments in the field of organic photovoltaics (efficiency>12%) in recent years has opened up a new possibility for the commercialization of low cost, flexible, and third generation photovoltaics. However, the rapid degradation of the organic materials and their short exciton diffusion lengths are major hindrance for the complete development of organic solar cells for commercial use. The concept of organic/inorganic hybrid solar cell which combines the advantages of both organic and inorganic materials are readily applicable for low cost, low temperature, high yield, and solution processable techniques but suffers from low fundamental efficiency. Recently, a new class of orgnanic/inorganic hybrid material known as organometal trihalide perovskites have emerged which exhibit the properties of good absorbtion, free charge carrier generation and efficient transport of the generated carriers while maintaining the primary requirements of organic electronics viz. low temperature and solution processability.In our present work, we have demonstrated the enhancement in device efficiency by incorporating organometal trihalide perovskite (CH3NH3PbI3) into ZnO nanostructured/MDMO-PPV inverted solar cell. The devices with perovskite absorbers showed a photocoversion efficiency of 1.97% in contrast to mere 0.06% obtained for ZnO/MDMO-PPV devices.

Amino‐Functionalized Conjugated Polymer as an Efficient Electron Transport Layer for High‐Performance Planar‐Heterojunction Perovskite Solar Cells

An amino‐functionalized copolymer with a conjugated backbone composed of fluorene, naphthalene diimide, and thiophene spacers (PFN‐2TNDI) is introduced as an alternative electron transport layer (ETL) to replace the commonly used [6,6]‐Phenyl‐C61‐butyric acid methyl ester (PCBM) in the p–i–n planar‐heterojunction organometal trihalide perovskite solar cells. A combination of characterizations including photoluminescence (PL), time‐resolved PL decay, Kelvin probe measurement, and impedance spectroscopy is used to study the interfacial effects induced by the new ETL. It is found that the amines on the polymer side chains not only can passivate the surface traps of perovskite to improve the electron extraction properties, they also can reduce the work function of the metal cathode by forming desired interfacial dipoles. With these dual functionalities, the resulted solar cells outperform those based on PCBM with power conversion efficiency (PCE) increased from 12.9% to 16.7% based on PFN‐2TNDI. In addition to the performance enhancement, it is also found that a wide range of thicknesses of the new ETL can be applied to produce high PCE devices owing to the good electron transport property of the polymer, which offers a better processing window for potential fabrication of perovskite solar cells using large‐area coating method.

Recent Advances in Improving the Stability of Perovskite Solar Cells

Organometal trihalide perovskites have recently emerged as promising materials for low‐cost, high‐efficiency solar cells. In less than five years, the efficiency of perovskite solar cells (PSC) has been updated rapidly as a result of new strategies adopted in their fabrication process, including device structure, interfacial engineering, chemical compositional tuning, and crystallization kinetics control. To date, the best PSC efficiency has reached 20.1%, which is close to that of single crystal silicon solar cells. However, the stability of PSC devices is still unsatisfactory and is the main bottleneck impeding their commercialization. Here, we summarize recent studies on the degradation mechanisms of organometal trihalide perovskites in PSC devices, and the strategies for stability improvement.

Microstructures of Organometal Trihalide Perovskites for Solar Cells: Their Evolution from Solutions and Characterization.

The use of organometal trihalide perovskites (OTPs) in perovskite solar cells (PSCs) is revolutionizing the field of photovoltaics, which is being led by advances in solution processing of OTP thin films. First, we look at fundamental phenomena pertaining to nucleation/growth, coarsening, and microstructural evolution involved in the solution-processing of OTP thin films for PSCs from a materials-science perspective. Established scientific principles that govern some of these phenomena are invoked in the context of specific literature examples of solution-processed OTP thin films. Second, the nature and the unique characteristics of OTP thin-film microstructures themselves are discussed from a materials-science perspective. Finally, we discuss the challenges and opportunities in the characterization of OTP thin films for not only gaining a deep understanding of defects and microstructures but also elucidating classical and nonclassical phenomena pertaining to nucleation/growth, coarsening, and microstructural evolution in these films. The overall goal is to have deterministic control over the solution-processing of tailored OTP thin films with desired morphologies and microstructures.

Ultrafast photomodulation spectroscopy of π-conjugated polymers, nanotubes and organometal trihalide perovskites: A comparison

We compare the ultrafast dynamics of the primary photoexcitations in various π-conjugated organic semiconductors, semiconducting single-walled carbon nanotubes (S-NTs) and organometal trihalide perovskites including CH3NH3PbI3 (MAPbI3) and CH3NH3PbI1.1Br1.9 (MAPbI1.1Br1.9), using broadband pump–probe photomodulation spectroscopy in the spectral range of 0.2–2.7eV with 300fs time resolution. The primary photoexcitations in single polymer chains and isolated S-NTs have been found to be quasi-one-dimensional (q-1D) excitons, with characteristic photoinduced absorption (PA) band due to intra-band transitions. This conclusion is in agreement with the large exciton binding energy, Eb in polymers and S-NTs (where Eb>200meV), illustrating the universal optical characteristic features of q-1D excitons. In three dimensional (3D) semiconductors of organometal trihalide perovskites such as MAPbI3 we found that with above-gap excitation both photo-carriers and excitons are photogenerated; but only photocarriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in MAPbI1.1Br1.9. The contrast between MAPbI3 and MAPbI1.1Br1.9 is ascribed to the difference of Eb, which is ∼20meV and ∼110meV, respectively. Our work shows that Eb is one of the crucial parameters that determine the photophysics characteristic of semiconductors, that result in universal occurrence of an exciton PA band, regardless if the compound is q-1D carbon based π-conjugated semiconductors, NTs, or 3D crystalline perovskite semiconductors. At the same time, our work also shows that the broadband ultrafast photomodulation spectroscopy is a powerful tool in analyzing the photophysics of semiconductors, and emphasizes the need for a broad probe spectral range in order to decipher the primary photoexcitation species.

Improving the Extraction of Photogenerated Electrons with SnO2 Nanocolloids for Efficient Planar Perovskite Solar Cells

Great attention to cost‐effective high‐efficiency solar power conversion of trihalide perovskite solar cells (PSCs) has been hovering at high levels in the recent 5 years. Among PSC devices, admittedly, TiO2 is the most widely used electron transport layer (ETL); however, its low mobility which is even less than that of CH3NH3PbI3 makes it not an ideal material. In principle, SnO2 with higher electron mobility can be regarded as a positive alternative. Herein, a SnO2 nanocolloid sol with ≈3 nm in size synthesized at 60 °C was spin‐coated onto the fuorine‐doped tin oxide (FTO) glass as the ETL of planar CH3NH3PbI3 perovskite solar cells. TiCl4 treatment of SnO2‐coated FTO is found to improve crystallization and increase the surface coverage of perovskites, which plays a pivotal role in improving the power conversion efficiency (PCE). In this report, a champion efficiency of 14.69% (Jsc = 21.19 mA cm−2, Voc = 1023 mV, and FF = 0.678) is obtained with a metal mask at one sun illumination (AM 1.5G, 100 mW cm−2). Compared to the typical TiO2, the SnO2 ETL efficiently facilitates the separation and transportation of photogenerated electrons/holes from the perovskite absorber, which results in a significant enhancement of photocurrent and PCE.

Perovskite Solar Cells: Light‐Induced Self‐Poling Effect on Organometal Trihalide Perovskite Solar Cells for Increased Device Efficiency and Stability (Adv. Energy Mater. 20/2015)

In article number 1500721, Jinsong Huang and co-workers report that ion migration can be driven by illumination-induced photovoltage in hybrid perovskite solar cells. As a result of photo-induced ion migration, both the power conversion efficiency and stability of perovskite solar cells are improved.

Influence of the additives in poly(3-hexylthiophene) hole transport layer on the performance of perovskite solar cells

The hybrid organic-inorganic methylammonium lead trihalide (CH3NH3PbI3-xClx) perovskite solar cells employing poly(3-hexylthiophene) (P3HT) hole transport layer with different doped amounts of bis(trifluoromethane) sulfonimide lithium salt (Li-TFSI) and 4-tert-butylpyridine (D-TBP) are fabricated. It is found that the doped amounts of Li-TFSI and D-TBP greatly affect the performance of the devices, such as surface coverage, Hall mobility and bulk concentration of P3HT films. The highest power conversion efficiency of 9.7% is obtained in optimal devices due to the enhanced charge transport and the reduced charge recombination at the interfaces of the devices. The best efficiency of the optimal devices with Li-TFSI and D-TBP is increased by ~90%, compared with the reference without additives.

Fabrication of efficient planar perovskite solar cells using a one-step chemical vapor deposition method.

Organometallic trihalide perovskites are promising materials for photovoltaic applications, which have demonstrated a rapid rise in photovoltaic performance in a short period of time. We report a facile one-step method to fabricate planar heterojunction perovskite solar cells by chemical vapor deposition (CVD), with a solar power conversion efficiency of up to 11.1%. We performed a systematic optimization of CVD parameters such as temperature and growth time to obtain high quality films of CH3NH3PbI3 and CH3NH3PbI3-xClx perovskite. Scanning electron microscopy and time resolved photoluminescence data showed that the perovskite films have a large grain size of more than 1 micrometer, and carrier life-times of 10 ns and 120 ns for CH3NH3PbI3 and CH3NH3PbI3-xClx, respectively. This is the first demonstration of a highly efficient perovskite solar cell using one step CVD and there is likely room for significant improvement of device efficiency.

Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites.

Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination

Organolead trihalide perovskite is an emerging low-cost, solution-processable material with a tunable bandgap from the violet to near-infrared, which has attracted a great deal of interest for applications in high-performance optoelectronic devices. Here, we present hybrid perovskite single-crystal photodetectors that have a very narrow spectral response with a full-width at half-maximum of <20 nm. The response spectra are continuously tuned from blue to red by changing the halide composition and thus the bandgap of the single crystals synthesized by solution processes. The narrowband photodetection can be explained by the strong surface-charge recombination of the excess carriers close to the crystal surfaces generated by short-wavelength light. The excess carriers generated by below-bandgap excitation locate away from the surfaces and can be much more efficiently collected by the electrodes, assisted by the applied electric field. This provides a new design paradigm for a narrowband photodetector with broad applications where background noise emission needs to be suppressed. Perovskite-based devices typically exhibit broadband spectral responses. Here narrowband (< 20 nm FWHM) response is achieved for a photodetector application.

Molecular Engineering of Functional Materials for Energy and Opto-Electronic Applications.

This review presents an overview of the dedicated research directions of the Group for Molecular Engineering of Functional Materials (GMF). This includes molecular engineering aspects of sensitizers constructed from ruthenium complexes, organic molecules, porphyrins and phthalocyanines. Manipulation of organometal trihalide perovskites, and charge transporting materials for high performance perovskite solar cells and photo-detectors are also described. Controlling phosphorescence color, and quantum yields in iridium complexes by tailoring ligands for organic light emitting diodes are demonstrated. Efficient reduction of CO(2) to CO using molecular catalyst on a protected Cu(2)O photocathode, and cost-effective water-splitting cell using a high efficiency perovskite solar cell are presented.

Light‐Induced Self‐Poling Effect on Organometal Trihalide Perovskite Solar Cells for Increased Device Efficiency and Stability

Light‐Induced Self‐Poling Effect on Organometal Trihalide Perovskite Solar Cells for Increased Device Efficiency and Stability