Mechanisms of charge accumulation in the dark operation of perovskite solar cells

In this work, a new current peak at forward bias in the dark current–voltage curves has been identified for standard mesoscopic perovskite solar cells. This characteristic peak appears only under some specific conditions, mainly in the reverse scan (RS) direction and when the solar cells were kept for several seconds under short-circuit conditions before starting the RS measurement. This peak disappears when the above experimental conditions are not applied. It is considered that this uncommon diode shape is obtained because shallow and/or deep trap states located at the interface between either perovskite/ p-type or perovskite/n-type transport materials are dynamically filled during the RS voltage scan. To corroborate this hypothesis, the response of hole tran sport materials (HTMs), small molecule spiro-OMeTAD and polymer P3HT, as well as both HTMs with additives, was compared. Also perovskite absorbers such as CH 3 NH 3 PbI 3 and all-inorganic perovskite based on cesium (CsPbI 3 ) were also analyzed, achieving in all cases similar trends.This research was supported by CRES

Tunable Open Circuit Voltage by Engineering Inorganic Cesium Lead Bromide/Iodide Perovskite Solar Cells

Perovskite solar cells based on series of inorganic cesium lead bromide and iodide mixture, CsPbBr3-xI x , where x varies between 0, 0.1, 0.2, and 0.3 molar ratio were synthesized by two step-sequential deposition at ambient condition to design the variations of wide band gap light absorbers. A device with high overall photoconversion efficiency of 3.98 % was obtained when small amount of iodide (CsPbBr2.9I0.1) was used as the perovskite and spiro-OMeTAD as the hole transport material (HTM). We investigated the origin of variation in open circuit voltage, Voc which was shown to be mainly dependent on two factors, which are the band gap of the perovskite and the work function of the HTM. An increment in Voc was observed for the device with larger perovskite band gap, while keeping the electron and hole extraction contacts the same. Besides, the usage of bilayer P3HT/MoO3 with deeper HOMO level as HTM instead of spiro-OMeTAD, thus increased the Voc from 1.16 V to 1.3 V for CsPbBr3 solar cell, although the photocurrent is lowered due to charge extraction issues. The stability studies confirmed that the addition of small amount of iodide into the CsPbBr3 is necessarily to stabilize the cell performance over time

Effect of Pristine Graphene on Methylammonium Lead Iodide Films and Implications on Solar Cell Performance

The relatively low stability of solar cells based on hybrid halide perovskites is the main issue to be solved for the implementation in real life of these extraordinary materials. Degradation is accelerated by temperature, moisture, oxygen, and light and mediated by halide easy hopping. The approach here is to incorporate pristine graphene, which is hydrophobic and impermeable to gases and likely limits ionic diffusion while maintaining adequate electronic conductivity. Low concentrations of few-layer graphene platelets (up to 24 × 10–3 wt %) were incorporated to MAPbI3 films for a detailed structural, optical, and transport study whose results are then used to fabricate solar cells with graphene-doped active layers. The lowest graphene content delays the degradation of films with time and light irradiation and leads to enhanced photovoltaic performance and stability of the solar cells, with relative improvement over devices without graphene of 15% in the power conversion efficiency, PCE. A higher graphene content further stabilizes the perovskite films but is detrimental for in-operation devices. A trade-off between the possible sealing effect of the perovskite grains by graphene, that limits ionic diffusion, and the reduction of the crystalline domain size that reduces electronic transport, and, especially, the detected increase of film porosity, that facilitates the access to atmospheric gases, is proposed to be at the origin of the observed trends. This work demonstrated how the synergy between these materials can help to develop cost-effective routes to overcome the stability barrier of metal halide perovskites, introducing active layer design strategies that allow commercialization to take off.We acknowledge financial support by the Spanish Ministry of Science and Innovation under Projects PID2020-115514RB-I00 (C.C.), MAT2015-65356-C3-2-R (A.A), and PID2019-107314RB-I00 (I.M-S). This work was partially supported by European Research Council (ERC) via Consolidator Grant (724424-No-LIMIT) (I.M-S), AYUDA PUENTE 2020 URJC (C.C.). Associated Lab LABCADIO belonging to Community of Madrid, CM, net laboratories ref 351 is also acknowledged (C.C.). T.S.R. acknowledges funding from CM and European Social Fund (ESF) under the Talento fellowship 2017-T2/IND-5586 and project F660 financed by CM and Rey Juan Carlos University under action 1, “Encouragement of Young Phd students investigation". C.R-O. acknowledges funding from the Spanish Ministry of Science and Innovation under a FPI predoctoral contract (PRE2019-088433)

Ultrafast selective extraction of hot holes from cesium lead iodide perovskite films

Lead halide perovskites have some unique properties which are very promising for optoelectronic applications such as solar cells, LEDs and lasers. One important and expected application of perovskite halide semiconductors is solar cell operation including hot carriers. This advanced solar cell concept allows overcoming the Shockley–Queisser efficiency limit, thereby achieving energy conversion efficiency as high as 66% by extracting hot carriers. Understanding ultrafast photoexcited carrier dynamics and extraction in lead halide perovskites is crucial for these applications. Here, we clarify the hot carrier cooling and transfer dynamics in all-inorganic cesium lead iodide (CsPbI3) perovskite using transient absorption spectroscopy and Al2O3, poly(3-hexylthiophene-2,5-diyl) (P3HT) and TiO2 as selective contacts. We find that slow hot carrier cooling occurs on a timescale longer than 10 ps in the cases of CsPbI3/Al2O3 and CsPbI3/ TiO2, which is attributed to hot phonon bottleneck for the high photoexcited carrier density. An efficient ultrafast hole transfer from CsPbI3 to the P3HT hole extracting layer is observed. These results suggest that hot holes can be extracted by appropriate selective contacts before energy dissipation into the halide perovskite lattice and that CsPbI3 has a potential for hot carrier solar cell applications

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

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%

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

Recombination study of combined halides (Cl, Br, I) perovskite solar cells

We report on the preparation of a series of solution-processed perovskite solar cells based on methylammonium (MA) lead halide derivatives, MAPbX 3, which show tunable optical properties depending on the nature and ratio of the halides employed (X = Cl, Br, and I). Devices have been prepared with different cell architecture, thin film, and mesoporous scaffold (TiO 2 and Al2O3). We have analyzed different sample sets focusing on the characterization of the charge recombination by means of impedance spectroscopy (IS). On the one hand, our study discloses that the insertion of both Cl and Br in the perovskite lattice reduces the charge recombination rates in the light absorber film, thus determining the open circuit voltage (Voc) of the device. The samples prepared on a mesoporous Al2O3 electrode present lower charge recombination rates than those devices prepared on mesoporous TiO2. Furthermore, the addition of Br in the perovskite structure was demonstrated to improve slightly the lifetime of the devices; in fact, the efficiencies of all devices tested remained at least at the 80% of the initial value 1 month after their preparation. These results highlight the crucial role of the charge-recombination processes on the performance of the perovskite solar cells and pave the way for further progress on this field.Fil: Suarez, Belen. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Universitat Jaume I; EspañaFil: Gonzalez-Pedro, Victoria. Universitat Jaume I; EspañaFil: Ripolles, Teresa S.. Universitat Jaume I; EspañaFil: Sanchez, Rafael S.. Universitat Jaume I; EspañaFil: Otero, Luis Alberto. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Austral de Investigaciones Científicas; ArgentinaFil: Mora-Sero, Ivan. Universitat Jaume I; Españ

Interface Engineering in Perovskite Solar Cells by Low Concentration of Phenylethyl Ammonium Iodide Solution in the Antisolvent Step

[EN] In spite of the outstanding properties of metal halide perovskites, its polycrystalline nature induces a wide range of structural defects that results in charge losses that affect the final device performance and stability. Herein, a surface treatment is used to passivate interfacial vacancies and improve moisture tolerance. A functional organic molecule, phenylethyl ammonium iodide (PEAI) salt, is dissolved with the antisolvent step. The additive used at low concentration does not induce formation of low-dimensional perovskites species. Instead, the organic halide species passivate the surface of the perovskite and grain boundaries, which results in an effective passivation. For sake of generality, this facile solution-processed synthesis was studied for halide perovskite with different compositions, the standard perovskite MAPbI, and double cation perovskites, MACsPbI and MAFAPbI, increasing the average photoconversion efficiency compared to the reference cell by 18%, 32%, and 4% respectively, observed for regular, n-i-p, and inverted, p-i-n, solar cell configurations. This analysis highlights the generality of this approach for halide perovskite materials in order to reduce nonradiative recombination as observed by impedance spectroscopy.T.S.R. acknowledges funding from Community of Madrid under the Talentfellowship 2017-T2/IND-5586 and project F660 financed by Community of Madrid and Rey Juan Carlos University. The authors acknowledgefinancialsupport by the Spanish Ministry of Science and Innovation under Projects PID2020-115514RB-I00, MAT2015-65356-C3-2-R, and PID2019-107314RB-I00. This work was partially supported by AYUDA PUENTE 2020 URJC.Associated Lab LABCADIO belonging to CM net laboratories ref 351are also acknowledge. C.R.O. acknowledges funding from the Spanish Ministry of Science and Innovation under a FPI pre-doctoral contract(PRE2019-088433

Tunable Open Circuit Voltage by Engineering Inorganic Cesium Lead Bromide/Iodide Perovskite Solar Cells

Abstract Perovskite solar cells based on series of inorganic cesium lead bromide and iodide mixture, CsPbBr3-x I x , where x varies between 0, 0.1, 0.2, and 0.3 molar ratio were synthesized by two step-sequential deposition at ambient condition to design the variations of wide band gap light absorbers. A device with high overall photoconversion efficiency of 3.98 % was obtained when small amount of iodide (CsPbBr2.9I0.1) was used as the perovskite and spiro-OMeTAD as the hole transport material (HTM). We investigated the origin of variation in open circuit voltage, V oc which was shown to be mainly dependent on two factors, which are the band gap of the perovskite and the work function of the HTM. An increment in V oc was observed for the device with larger perovskite band gap, while keeping the electron and hole extraction contacts the same. Besides, the usage of bilayer P3HT/MoO3 with deeper HOMO level as HTM instead of spiro-OMeTAD, thus increased the V oc from 1.16 V to 1.3 V for CsPbBr3 solar cell, although the photocurrent is lowered due to charge extraction issues. The stability studies confirmed that the addition of small amount of iodide into the CsPbBr3 is necessarily to stabilize the cell performance over time