Yaohong Zhang

Colloidal Synthesis of Air-Stable Alloyed CsSn1–xPbxI3 Perovskite Nanocrystals for Use in Solar Cells

Organic-inorganic hybrid perovskite solar cells have demonstrated unprecedented high power conversion efficiencies in the past few years. Now, the universal instability of the perovskites has become the main barrier for this kind of solar cells to realize commercialization. This situation can be even worse for those tin-based perovskites, especially for CsSnI3, because upon exposure to ambient atmosphere the desired black orthorhombic phase CsSnI3 would promptly lose single crystallinity and degrade to the inactive yellow phase, followed by irreversible oxidation into metallic Cs2SnI6. By alloying CsSnI3 with CsPbI3, we herein report the synthesis of alloyed perovskite quantum dot (QD), CsSn1-xPbxI3, which not only can be phase-stable for months in purified colloidal solution but also remains intact even directly exposed to ambient air, far superior to both of its parent CsSnI3 and CsPbI3 QDs. Ultrafast transient absorption spectroscopy studies reveal that the photoexcited electrons in the alloyed QDs can be injected into TiO2 nanocrystals at a fast rate of 1.12 × 1011 s-1, which enables a high photocurrent generation in solar cells.

Fabrication of YxBi1−xVO4 solid solutions for efficient C2H4 photodegradation

Photocatalytic oxidation of ethylene continues to be a challenge at the frontier of chemistry. Previous investigations have shown that BiVO4 possesses strong photo-oxidative properties which can efficiently oxidize water and decompose organics in aqueous solutions; however, its conduction band minimum is too low to utilize the photo-generated electrons. Herein we report for the first time its effects on gaseous C2H4 photo-oxidation by fabricating YxBi1−xVO4 (x = 0.00–1.00) semiconductors with a polymeric method. Phase analysis identified that there are both a region of monoclinic and tetragonal phase coexistence (0.05 ≤ x ≤ 0.45) and a solid solution region (0.5 ≤ x ≤ 1.0). UV-visible diffusive reflectance spectra and Mott–Schottky analysis revealed that the incorporation of Y3+ widened the band gap by shifting upward the conduction band minimum as well as shifting downward the valance band maximum. Remarkable C2H4 photodegradation was obtained upon the Y0.85Bi0.15VO4 photocatalyst and its superior performance is ascribed to the synergistic effect of C2H4 adsorption, active oxygen species ˙O2− utilization, and relatively large surface area. The present study will be valuable for further investigation on both BiVO4 and hydrocarbons (HC) degradation.

Mixed Sn–Ge Perovskite for Enhanced Perovskite Solar Cell Performance in Air

Lead-based perovskite solar cells have gained ground in recent years, showing efficiency as high as 20%, which is on par with that of silicon solar cells. However, the toxicity of lead makes it a nonideal candidate for use in solar cells. Alternatively, tin-based perovskites have been proposed because of their nontoxic nature and abundance. Unfortunately, these solar cells suffer from low efficiency and stability. Here, we propose a new type of perovskite material based on mixed tin and germanium. The material showed a band gap around 1.4-1.5 eV as measured from photoacoustic spectroscopy, which is ideal from the perspective of solar cells. In a solar cell device with inverted planar structure, pure tin perovskite solar cell showed a moderate efficiency of 3.31%. With 5% doping of germanium into the perovskite, the efficiency improved up to 4.48% (6.90% after 72 h) when measured in air without encapsulation.

Slow hot carrier cooling in cesium lead iodide perovskites

Lead halide perovskites are attracting a great deal of interest for optoelectronic applications such as solar cells, LEDs, and lasers because of their unique properties. In solar cells, heat dissipation by hot carriers results in a major energy loss channel responsible for the Shockley–Queisser efficiency limit. Hot carrier solar cells offer the possibility to overcome this limit and achieve energy conversion efficiency as high as 66% by extracting hot carriers. Therefore, fundamental studies on hot carrier relaxation dynamics in lead halide perovskites are important. Here, we elucidated the hot carrier cooling dynamics in all-inorganic cesium lead iodide (CsPbI3) perovskite using transient absorption spectroscopy. We observe that the hot carrier cooling rate in CsPbI3 decreases as the fluence of the pump light increases and the cooling is as slow as a few 10 ps when the photoexcited carrier density is 7 × 1018 cm−3, which is attributed to phonon bottleneck for high photoexcited carrier densities. Our findings suggest that CsPbI3 has a potential for hot carrier solar cell applications.

Understanding charge transfer and recombination by interface engineering for improving the efficiency of PbS quantum dot solar cells

In quantum dot heterojunction solar cells (QDHSCs), the QD active layer absorbs sunlight and then transfers the photogenerated electrons to an electron-transport layer (ETL). It is generally believed that the conduction band minimum (CBM) of the ETL should be lower than that of the QDs to enable efficient charge transfer from the QDs to the collection electrode (here, FTO) through the ETL. However, by employing Mg-doped ZnO (Zn1-xMgxO) as a model ETL in PbS QDHSCs, we found that an ETL with a lower CBM is not necessary to realize efficient charge transfer in QDHSCs. The existence of shallow defect states in the Zn1-xMgxO ETL can serve as additional charge-transfer pathways. In addition, the conduction band offset (CBO) between the ETL and the QD absorber has been, for the first time, revealed to significantly affect interfacial recombination in QDHSCs. We demonstrate that a spike in the band structure at the ETL/QD interface is useful for suppressing interfacial recombination and improving the open-circuit voltage. By varying the Mg doping level in ZnO, we were able to tune the CBM, defect distribution and carrier concentration in the ETL, which play key roles in charge transfer and recombination and therefore the device performance. PbS QDHSCs based on the optimized Zn1-xMgxO ETL exhibited a high power conversion efficiency of 10.6%. Our findings provide important guidance for enhancing the photovoltaic performance of QD-based solar cells.

Ultrafast Electron Injection from Photoexcited Perovskite CsPbI3 QDs into TiO2 Nanoparticles with Injection Efficiency near 99

Photoexcited electron injection dynamics from CsPbI3 quantum dots (QDs) to wide gap metal oxides are studied by transient absorption spectroscopy. Experimental results show under a low excitation intensity that ∼99% of the photoexcited electrons in CsPbI3 QDs can be injected into TiO2 with a size-dependent rate ranging from 1.30 × 1010 to 2.10 × 1010 s-1, which is also ∼2.5 times faster than that in the case of ZnO. A demonstration QD-sensitized solar cell based on a CsPbI3/TiO2 electrode is fabricated that delivers a power conversion efficiency of 5%.

Hindered Formation of Photoinactive δ-FAPbI3 Phase and Hysteresis-Free Mixed-Cation Planar Heterojunction Perovskite Solar Cells with Enhanced Efficiency via Potassium Incorporation

Organic-inorganic hybrid lead halide perovskite solar cells have demonstrated competitive power conversion efficiency over 22%; nevertheless, critical issues such as unsatisfactory device stability, serious current-voltage hysteresis, and formation of photo nonactive perovskite phases are obstacles for commercialization of this photovoltaics technology. Herein we report a facial yet effective method to hinder formation of photoinactive δ-FAPbI3 and hysteresis behavior in planar heterojunction perovskite solar cells based on K x(MA0.17FA0.83)1- xPbI2.5Br0.5 (0≤ x ≤ 0.1) through incorporation of potassium ions (K+). X-ray diffraction patterns demonstrate formation of photoinactive δ-FAPbI3 was almost completely suppressed after K+ incorporation. Density functional theory calculation shows K+ prefers to enter the interstitial sites of perovskite lattice, leading to chemical environmental change in the crystal structure. Ultrafast transient absorption spectroscopy has revealed that K+ incorporation leads to enhanced carrier lifetime by 50%, which is also confirmed by reduced trap-assisted recombination of the perovskite solar cells containing K+ in photovoltage decay. Ultraviolet photoelectron spectroscopy illustrates that K+ incorporation results in a significant rise of conduction band minimum of the perovskite material by 130 meV, leading to a more favorable energy alignment with electron transporting material. At the optimal content of 3% K+ (molar ratio, relative to the total monovalent cations), nearly hysteresis-free, enhanced power conversion efficiencies from 15.72% to 17.23% were obtained in this solar cell.

Lead Selenide Colloidal Quantum Dot Solar Cells Achieving High Open-Circuit Voltage with One-Step Deposition Strategy

Lead selenide (PbSe) colloidal quantum dots (CQDs) are considered to be a strong candidate for high-efficiency colloidal quantum dot solar cells (CQDSCs) due to its efficient multiple exciton generation. However, currently, even the best PbSe CQDSCs can only display open-circuit voltage ( Voc) about 0.530 V. Here, we introduce a solution-phase ligand exchange method to prepare PbI2-capped PbSe (PbSe-PbI2) CQD inks, and for the first time, the absorber layer of PbSe CQDSCs was deposited in one step by using this PbSe-PbI2 CQD inks. One-step-deposited PbSe CQDs absorber layer exhibits fast charge transfer rate, reduced energy funneling, and low trap assisted recombination. The champion large-area (active area is 0.35 cm2) PbSe CQDSCs fabricated with one-step PbSe CQDs achieve a power conversion efficiency (PCE) of 6.0% and a Voc of 0.616 V, which is the highest Voc among PbSe CQDSCs reported to date.

All‐Inorganic CsPb1−xGexI2Br Perovskite with Enhanced Phase Stability and Photovoltaic Performance

Compared with organic-inorganic perovskites, all-inorganic cesium-based perovskites without volatile organic compounds have gained extensive interests because of the high thermal stability. However, they have a problem on phase transition from cubic phase (active for photo-electric conversion) to orthorhombic phase (inactive for photo-electric conversion) at room temperature, which has hindered further progress. Herein, novel inorganic CsPb1-x Gex I2 Br perovskites were prepared in humid ambient atmosphere without a glovebox. The phase stability of the all-inorganic perovskite was effectively enhanced after germanium addition. In addition, the highest power conversion efficiency of 10.8 % with high open-circuit voltage (VOC ) of 1.27 V in a planar solar cell based on CsPb0.8 Ge0.2 I2 Br perovskite was achieved. Furthermore, the highest VOC up to 1.34 V was obtained by CsPb0.7 Ge0.3 I2 Br perovskite, which is a remarkable record in the field of all-inorganic perovskite solar cells. More importantly, all the photovoltaic parameters of CsPb0.8 Ge0.2 I2 Br perovskite solar cells showed nearly no decay after 7 h measurement in 50-60 % relative humidity without encapsulation.

Recombination Suppression in PbS Quantum Dot Heterojunction Solar Cells by Energy-Level Alignment in the Quantum Dot Active Layers

Using spatial energy-level gradient engineering with quantum dots (QDs) of different sizes to increase the generated carrier collection at the junction of a QD heterojunction solar cell (QDHSC) is a hopeful route for improving the energy-conversion efficiency. However, the results of current related research have shown that a variable band-gap structure in a QDHSC will create an appreciable increase, not in the illumination current density, but rather in the fill factor. In addition, there are a lack of studies on the mechanism of the effect of these graded structures on the photovoltaic performance of QDHSCs. This study presents the development of air atmosphere solution-processed TiO2/PbS QDs/Au QDHSCs by engineering the energy-level alignment (ELA) of the active layer via the use of a sorted order of differently sized QD layers (four QD sizes). In comparison to the ungraded device (without the ELA), the optimized graded architecture (containing the ELA) solar cells exhibited a great increase (21.4%) in short-circuit current density ( Jsc). As a result, a Jsc value greater than 30 mA/cm2 has been realized in planar, thinner absorption layer (∼300 nm) PbS QDHSCs, and the open-circuit voltage ( Voc) and power-conversion efficiency (PCE) were also improved. Through characterization by the light intensity dependences of the Jsc and Voc and transient photovoltage decay, we find that (i) the ELA structure, serving as an electron-blocking layer, reduces the interfacial recombination at the PbS/anode interface, and (ii) the ELA structure can drive more carriers toward the desirable collection electrode, and the additional carriers can fill the trap states, reducing the trap-assisted recombination in the PbS QDHSCs. This work has clearly elucidated the mechanism of the recombination suppression in the graded QDHSCs and demonstrated the effects of ELA structure on the improvement of Jsc. The charge recombination mechanisms characterized in this work would be able to shed light on further improvements of QDHSCs, which could even benefit other types of solar cells.