Organic-inorganic Hybrid Perovskite Research Articles

A Scorpion–Type Dopant‐Free Hole Transport Material for n‐i‐p Organic–Inorganic Hybrid Perovskite Solar Cells

AbstractIt is significant to develop dopant‐free hole transport materials (HTMs) to improve the long‐term stability of n‐i‐p organic–inorganic hybrid perovskite solar cells (PSCs). In this work, two HTMs (DTTP‐T and DTTP‐D) based on dithienothiopyrrole (DTTP) core were synthesized to explore the effects of different substituents on the nitrogen atom on the properties of HTMs. Compared with anisole‐substituted DTTP‐D, triarylamine‐substituted scorpion‐type DTTP‐T shows better matching energy level, stronger charge transfer and defect passivation ability. Therefore, the power conversion efficiency (PCE) of dopant‐free DTTP‐T‐based n‐i‐p PSCs reaches 18.67 %, which is comparable to that of doped Spiro‐OMeTAD (19.51 %). More encouragingly, the efficiency of DTTP‐T‐based devices remains above 80 % of its initial efficiency after 1728 h of storage in air, while the Spiro‐OMeTAD‐based devices could only maintain 600 h. This work provides a good reference for the development of dopant‐free small molecular HTMs for efficient and stable PSCs.

Conformational Disordering of Organic Cations during Moisture-Induced Structural Collapse in Organic–Inorganic Hybrid Perovskites

Conformational Disordering of Organic Cations during Moisture-Induced Structural Collapse in Organic–Inorganic Hybrid Perovskites

Elucidating the Interplay between Symmetry Distortions in Passivated MAPbI3 and the Rashba Splitting Effect.

Hybrid organic-inorganic perovskites play a critical role in modern optoelectronic applications, particularly as single photon sources due to their unusual bright ground state. However, the presence of trap states resulting from surface dangling bonds hinders their widespread commercial application. This work uses density functional theory (DFT) to study the effects of various passivating ligands and their binding sites on Rashba splitting, a phenomenon directly linked to the bright ground state. Our results predict that X2- and X4-type ligands that adsorb at acidic oxygen binding sites and zwitterionic binding sites efficiently eliminate trap states introduced by surface iodine vacancies. Furthermore, our results show that distortions from the nominally symmetric cubic structure of the perovskite predominantly determine the presence and magnitude of the Rashba splitting. Specifically, the loss of more symmetry elements consistently leads to Rashba splitting in both the valence band (VB) and the conduction band (CB) with small Rashba splitting coefficients. Conversely, although inversion symmetry breaking alone fails to guarantee the presence of pure Rashba splitting in both the VB and the CB, it significantly increases the degree of splitting. The adsorption of ligands not only mitigates trap states but also plays a critical role in altering the local symmetry, thus influencing Rashba splitting. DFT predicts a distinct Rashba-Dresselhaus splitting in the CB with X2 ligands, causing the largest splitting. The presence of local electric fields causes consistent Rashba splitting of the VB across all studied systems except for the X4 zwitterionic passivated systems (sulfobetaine and lecithin). Electric fields are predicted to cause significant splitting of the CB, particularly for MAPbI3 and SH passivated MAPbI3 surfaces that possess freely rotating ligand binding sites. This study reveals that the wavelength, tunability of Rashba splitting through an applied electric field, and nature of Rashba-Dresselhaus splitting are influenced by the characteristics of the ligand binding site. On the other hand, pure Rashba splitting is predicted to exhibit a greater susceptibility to symmetry distortion than to specific ligand binding sites. These findings elucidate how surface passivating ligands and symmetry distortions influence Rashba splitting, shaping the optoelectronic properties of perovskite nanocrystals.

Organic-Inorganic Hybrid Perovskite for Ferroelectric Catalysis.

Organic-inorganic hybrid perovskite ferroelectric has gained significant attention for its structural flexibility and diversity. They can directly utilize metal nodes and organic groups as active sites in catalysis. Additionally, their ferroelectric polarization occurs around these active sites, significantly enhancing catalytic activity and demonstrating immense potential for applications. However, their catalytic applications remain underexplored. This work marks the first utilization of the molecular perovskite ferroelectric [3,3-difluorocyclobutylammonium]2CuCl4 (Cu-DFCBA) as a catalyst for alkane oxidation. Under ultrasonic stimulation, it achieved a remarkable turnover number as high as 2402. Compared to inorganic ferroelectrics like lithium niobate (LiNbO3), the molecular ferroelectric exhibited a 1200-fold increase in catalytic activity. This highlights Cu-DFCBA's robust ferroelectric properties and underscores the vast potential of molecular ferroelectrics in catalysis, guiding future system designs.

Research on PbTiO3 nanoparticles optimized mesoporous layer for perovskite solar cells

Organic-inorganic hybrid perovskite solar cells have garnered significant attention due to their facile fabrication process and high photovoltaic conversion efficiency. The electron transport layer plays a crucial role in the carrier separation mechanism of perovskite solar cells, making it a focal point for enhancing cell performance. In this study, PbTiO3 was introduced into TiO2 mesoporous layers by modification and doping in order to optimize cell performance. Initially, the use of PbTiO3-modified mesoporous layers revealed issues such as non-uniform modification layers, low film coverage rates, and reduced light transmittance. These issues hindered the ability of PbTiO3 to facilitate carrier separation and resulting in suboptimal optimization effects. However, by utilizing PbTiO3-doped mesoporous layers for optimizing cell performance, we observed improved quality and higher light transmittance in the perovskite films. As a consequence of the improved carrier separation achieved by PbTiO3, the efficiency of the solar cell has been enhanced to 5.51%.

Enhancing Stability in All-Vacuum-Evaporated Hybrid Perovskite Solar Cells via a Bipolar Host as a Hole-Transporting Layer.

Growing an ultrathin hybrid organic-inorganic perovskite film while maintaining high efficiency and addressing photostability challenges for commercial devices remains a significant hurdle. In this study, we explore the incorporation of organometallic copper phthalocyanine (CuPc) and MS-OC (a previously published spiro-based interfacial material for perovskite solar cells (PSCs), featuring an ortho-oriented carbazole donor) as an addition to the hole-transporting layer (HTL) in all-vacuum-deposited Cs0.06FA0.94Pb(I0.68Br0.32)3 PSCs. By innovatively introducing a 3 nm-thin MS-OC layer at the CuPc-perovskite interface, we achieve a deeper understanding of the crystallographic dynamics of perovskites, resulting in a uniform and pinhole-free film. We demonstrate that PSCs utilizing the CuPc HTL with an MS-OC interfacial layer in a p-i-n architecture achieve a power conversion efficiency (PCE) of up to 14.42%. Remarkably, the CuPc/MS-OC-based device exhibits outstanding long-term photostability, maintaining its initial PCE over 400 h (T100 = 400 h) under continuous sunlight illumination. By configuring the device architecture as ITO/MoO3/CuPc/MS-OC/perovskite/C60/BCP/Ag, we find that the evaporated MS-OC thin films effectively reduce nonradiative losses, passivate the perovskite, and enhance device performance. Our findings indicate that the polarity of the underlying surface significantly influences perovskite nucleation, underscoring the potential to improve photostability by controlling interfacial imperfections.

A review of the progress of metal-organic frameworks in perovskite solar cells

Organic-inorganic hybrid perovskite solar cells (PSCs) have emerged as substantial challenges for future generations of photovoltaic apparatus, largely attributed to their power conversion efficiency (PCE) drastically elevated from below 10% to a staggering 25.7% over the past decade. Owing to characteristics distinct to them like substantial specific surface areas, copious binding locations, adjustable nanostructures, and mutual reinforcement, metal-organic frameworks (MOFs) are commonly utilized as either supplementary components or operational layers for augmenting both the efficiency and durability of PSCs. This paper primarily underlines the recent advancements in implementing MOFs across various operational strata of a PSC. The focal points of this study encompass an examination of the photovoltaic yields, the repercussions, and the advantages of fusing MOF materials into constituents like perovskite absorbers, electron transport, and hole transport layers, in addition to interface layers. The study also extends to an exploration of how MOFs effectively inhibit leakages of Pb2+ within halide perovskites and their associated apparatus. This paper concludes by discerning and shedding light on potential research prospects for the deployment of MOFs in PSCs.

Recent Advances in Organic Photodetectors

Organic photodetectors (OPDs) have garnered significant attention in fields such as image sensing, health monitoring, and wearable devices due to their exceptional performance. This review summarizes recent research advancements in materials, structures, performance, and applications of narrowband organic photodetectors, hybrid organic–inorganic perovskite photodetectors, flexible organic photodetectors (FOPDs), and photomultiplication type organic photodetectors (PM-OPDs). Organic semiconductors offer substantial potential in optoelectronic devices owing to their low cost, ease of processing, and tunable spectral response. Hybrid perovskite materials extend the spectral response range, FOPDs meet the demands of wearable devices, and PM-OPDs enhance sensitivity, allowing for the detection of weak light signals. Through innovations in materials, structural optimization, and improvements in manufacturing processes, the performance of OPDs has seen significant enhancement. This article also explores the application prospects of these technologies in medical monitoring, optical communications, and image sensing.

Transient Exciton-Charge Interconversion in Single-Crystal Hybrid Perovskites.

Ultrafast oscillatory transient absorption (TA) dynamics are observed in single crystals of hybrid organic-inorganic perovskite (CH3NH3)PbX3 with X = I, Br, Cl. High-density photoinduced charges, low binding energy of the excitons, efficient generation and high mobility of charges, and long diffusion length of both excitons and charges led to transient interconversion between excitons and charges with high efficiency, which is responsible for the oscillatory TA dynamics at re-excitation by the probe pulses. The pump pulses initiated a quasi-equilibrium scheme of coexisting excitons and charges with high densities, the probe pulse triggered a perturbation through interconversion between these two kinds of excited "particles," which was overlapped on the intrinsic exciton relaxation dynamics, producing an oscillatory modulation with time delay. This not only reveals important photoelectronic processes with determined time scales, but also supplies physics for applications of this group of materials.

Lead-Free Hybrid Perovskite: An Efficient Room-Temperature Spin Generator via Large Interfacial Rashba Effect.

Two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) shows great potential for developing flexible and wearable spintronic devices by serving as spin sources via the bulk Rashba effect (BRE). However, the practical application of BRE in 2D HOIP faces huge challenges, particularly due to the toxicity of lead, which is crucial for achieving large spin-orbit coupling, and the restrictions in 2D HOIP candidates to meet specific symmetry-breaking requirements. To overcome these obstacles, we designed a strategy to exploit the interfacial Rashba effect (IRE) of lead-free 2D HOIP (C6H5CH2CH2NH3)2CuCl4 (PEA-CuCl), manifesting as an efficient spin generator at room temperature. IRE of PEA-CuCl originates from the large orbital hybridization at the interface between PEA-CuCl and adjacent ferromagnetic layers. Spin-torque ferromagnetic resonance measurements further quantify a large Rashba effective field of 14.04 Oe per 1011 A m-2, surpassing those of lead-based HOIP and traditional all-inorganic heterojunctions with noble metals. Our lead-free 2D HOIP PEA-CuCl, which harnesses large IRE for spin generation, is efficient, nontoxic, and economic, offering huge promise for future flexible and wearable spintronic devices.

Violet Perovskite Quantum Dots of MA3Bi2Br9 and MA3Bi2Br6Cl3 Synthesized by the Cb‐LARP Method with Tunable Emission Wavelengths in Range of 379–400 nm

AbstractViolet‐emitting perovskite quantum dots (QDs) are of great significance for theoretical and experimental research aimed at promoting the development of environmentally friendly violet light‐emitting diodes (LEDs). Nevertheless, the synthesis of violet perovskite QDs via ligand‐assisted reprecipitation is challenging due to the significant bandgap. A simple and economical cryo‐bonding ligand‐assisted reprecipitation (Cb‐LARP) method is proposed as a means of synthesizing deep violet lead‐free organic‐inorganic hybrid perovskite (OIHP) QDs, with the objective of increasing the bandgap in the material. The MA3Bi2Br9 QDs synthesized by the Cb‐LARP method exhibit bright violet luminescence at 400 nm, with a PLQY of 50.1%. Moreover, the photoluminescence peak of the QDs can be adjusted from 402 to 393 nm by modifying the final reaction time. It is noteworthy that the MA3Bi2Br6Cl3 QDs exhibited ultraviolet emission at 379 nm, corresponding to a PLQY of 35.4%. Similarly, the emission peak of the QDs can be tuned from 379 to 376 nm by changing the final reaction time. The results demonstrate that the deep violet emitting OIHP QDs have been successfully synthesized. This study provides a theoretical reference for short‐wavelength perovskite materials and an experimental reference for the study of violet and UV quantum‐dot light‐emitting diode devices.

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two-Dimensional Hybrid Perovskite Photocatalysts.

Two-dimensional organic-inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron-hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4- octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non-overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

Formamidinium Incorporates into Rb‐based Non‐perovskite Phases in Solar Cell Formulations

Organic–inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI3), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non‐perovskite phase complicates the application of FAPbI3 in solar cells. To remedy this, alkali metal cations, most often Cs+, Rb+or K+, are included during perovskite synthesis to stabilize the photoactive phase. The atomic‐level mechanisms of stabilization are complex. While Cs+ dopes directly into the perovskite lattice, Rb+ does not, but instead forms an additional non‐perovskite phase, and the mechanism by which Rb confers increased stability remains unclear. Here, we use 1H–87Rb double resonance NMR experiments to show that FA+ incorporates into the Rb‐based non‐perovskite phases (FAyRb1‐yPb2Br5 and δ‐FAyRb1‐yPbI3) for both bromide and iodide perovskite formulations. This is demonstrated by changes in the 1H and 87Rb chemical shifts, 1H–87Rb heteronuclear correlation spectra, and 87Rb{1H} REDOR spectra. Simulation of the REDOR dephasing curves suggests up to ~60% FA+ incorporation into the inorganic Rb‐based phase for the bromide system. In light of these results, we hypothesize that the substitution of FA+ into the non‐perovskite phase may contribute to the greater stability conferred by Rb salts in the synthesis of FA‐based perovskites.

Formamidinium Incorporates into Rb-based Non-perovskite Phases in Solar Cell Formulations.

Organic-inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI3), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non-perovskite phase complicates the application of FAPbI3in solar cells. To remedy this, alkali metal cations, most often Cs+, Rb+or K+, are included during perovskite synthesis to stabilize the photoactive phase. The atomic-level mechanisms of stabilization are complex. While Cs+dopes directly into the perovskite lattice, Rb+does not, but instead forms an additional non-perovskite phase, and the mechanism by which Rb confers increased stability remains unclear. Here, we use1H-87Rb double resonance NMR experiments to show that FA+incorporates into the Rb-based non-perovskite phases (FAyRb1-yPb2Br5andδ-FAyRb1-yPbI3) for both bromide and iodide perovskite formulations. This is demonstrated by changes in the1H and87Rb chemical shifts,1H-87Rb heteronuclear correlation spectra, and87Rb{1H} REDOR spectra. Simulation of the REDOR dephasing curves suggests up to ~60% FA+incorporation into the inorganic Rb-based phase for the bromide system. In light of these results, we hypothesize that the substitution of FA+into the non-perovskite phase may contribute to the greater stability conferred by Rb salts in the synthesis of FA-based perovskites.

Polymer‐Assisted Nucleation for Stable Single‐Crystal Perovskite Thin Films

Organic–inorganic hybrid perovskite single crystals have emerged as a strong candidate in photovoltaic and general optoelectronic applications. However, the high supersaturation of the precursor solution leads to the rapid formation of a significant number of nuclei and a diminished concentration of perovskite solute. Consequently, the inadequate availability of precursors poses challenges in sustaining the subsequent crystal growth phase, culminating in the development of small‐sized single crystals. In this work, we report a controlled nucleation process to foster the growth of large‐size single crystals. This method through the coordination interaction between polyacrylic acid and Pb2+ ions, and substitution of the coordination with I‐ ions. This reduces the formation of the Pb‐I6 complex, which promptly emerges in a state of supersaturation and acts as a nucleus, thereby effectively reducing the number of nuclei formed. The single crystals produced using this method exhibit a lateral size exceeding 5 mm, an extended absorption range, a longer carrier lifetime of 10.93 ns, and enhanced stability. These crystals demonstrate the ability to remain stable even after storage in an ambient environment (T = 20 ± 5 °C, RH = 60 ± 5 %) for a period of 20 days.

A Prediction of All-Inorganic Lead-Free Halide Perovskites for Photovoltaic Application: Rb3Mo2Br9 and Rb3Mo2Cl9.

Lead-based organic-inorganic hybrid perovskites show promise as photovoltaic materials due to their high energy conversion efficiencies. However, concerns regarding lead toxicity and the poor environmental and operational stability of the organic cationic group have limited their widespread application. To address these challenges, the design of all-inorganic lead-free halide perovskites offers potential solutions for photovoltaic applications. Here, two layered perovskite derivatives, Rb3Mo2Cl9 and Rb3Mo2Br9, are explored, and their electronic, structural, and photovoltaic properties are analyzed using advanced theoretical calculations. Rb3Mo2Br9 exhibits a suitable direct bandgap of 1.60eV, making it a promising candidate for use as a light absorber in low-cost, high-efficiency solar cells. On the other hand, Rb3Mo2Cl9 demonstrates a wide direct bandgap exceeding 1.70eV, positioning it as a viable option for use as a top cell in tandem photovoltaic systems alongside silicon. Both materials display ideal optical properties in the visible light region and hold promise as excellent inorganic lead-free perovskite alternatives.

Dibenzothiophene S, S-Dioxide-Containing Dipolar Molecules As Efficient Hole-Transport Materials for p-i-n Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (OIH-PSCs) have developed rapidly in the past decade, and the commercialization of OIH-PSCs demands low-cost hole-transport materials (HTMs) with high performance and stability. The present study synthesized two organic HTMs containing dibenzothiophene S-dioxide as the acceptor unit and triphenylamine as the donor (denoted by TPAF-SO2 and TPA-SO2). In TPAF-SO2, the methoxy group and adjacent fluorine atom were introduced to decrease the highest occupied molecular orbital energy level. In TPA-SO2, the methyl sulfide group is the end group that can passivate the lead ion. TPAF-SO2 and TPA-SO2 exhibit hole-transport mobilities as high as 1.12 × 10-3 and 2.31 × 10-3 cm2 v-1 s-1, respectively, and strongly passivate Pb vacancies. Compared with TPAF-SO2, TPA-SO2 is more suitable for the growth of perovskite crystals. The perovskite grown on the latter has a lower trap density and higher carrier mobility; thus, both the nonradiative recombination and the charge-transport loss are decreased. The OIH-PSC based on TPA-SO2 as the HTM achieved a power conversion efficiency (PCE) as high as 22.08%, whereas the device based on TPAF-SO2 achieved a PCE of only 18.42%. In addition, the unencapsulated device based on TPA-SO2 can maintain 85% of the initial PCE after being stored in N2 for 1200 h, whereas the device based on TPAF-SO2 decayed rapidly to zero in 800 h under the same conditions.

Enhancing light trapping for improved efficiency of perovskite solar cells: design and analysis

Abstract A hybrid organic-inorganic perovskite solar cells (PSCs) is explored for its potential to achieve high-efficiency and cost-effective solar energy conversion, especially through improved light management. In this paper, COMSOL Multiphysics is utilized to explore PSCs with light trapping nanostructures which will enhance the optical and electrical properties. A nanometer-scale concave structure is proposed in this paper to direct and capture light. This configuration is compared to a planar structure to see how it affect PSCs optoelectronic performance. Electrical simulations showed that concave nanostructured PSCs increase carrier generation and collect more carriers. The short-circuit current rose from 3.91 mA for the planar structure to 4.95 mA for the concave structure. Power conversion efficiency for concave PSCs increased 11% compared to the planar construction after choosing optimal height of concave structure. Thus, the performance investigation by combined optical and electrical analysis of nanostructures shows that it has the ability to build high-efficiency PSCs with light-trapping approach.

Histidine-based hybrid perovskites as promising materials for wide wavelength photodetection

Layered 2D hybrid organic-inorganic perovskites (2D-HOIPs) exhibit a distinctive array of properties, including remarkable structural flexibility, enhanced resistance to moisture, and optoelectronic characteristics valuable for practical applications. Consequently, these materials are now widely acknowledged as pivotal components in optical and optoelectronic technologies. However, a significant drawback of 2D-HOIPs is their wide band gaps that has hindered their widespread application in optoelectronic devices. In this work we address this limitation by offering a novel series of 2D mixed-halide tin-based HOIPs with general formula (L-HisH)2SnBrxI4−x (where L-His = L-histidine, x = 4, 3.37, 1.70, 0.56, 0.44, and 0) for which the band gap can reach record narrow values, which are not typical for 2D-HOIPs. These compounds can be easily obtained in wide compositional range by implementing halide substitution approach. Each hybrid perovskite features a chiral structure imparted by chiral L-histidinium(+) cations interleaved between corner-shared tin halide octahedra, organized into single-layer thin inorganic slabs. Crucially, these new materials provide a high degree of flexibility in tuning their band gaps throughout the entire visible light spectrum, encompassing a range between 1.82 and 3.05 eV. As a “proof-of-concept”, we created a prototype HOIPs photodetector in which this HOIP was used as an active layer. It is noteworthy that the band gap of pure iodide perovskite is surprisingly narrow for this class of materials. The production of semiconductor materials with a variable width of the optical bandgap is the key to more versatile and diverse applications of these materials in the active components of modern optoelectronic devices. For the obtained prototype, light detection is observed in the wide range covering UV, visible and near-IR regions, marking a record achievement for 2D-HOIPs. Beyond photodetectors, these new histidine-based perovskites hold promise for applications in various other optoelectronic devices, including solar cells, photodiodes, phototransistors, polarized light detectors, and more.

Intercalation Electrode and Grain Reconstruction Induce Significant Sensitivity Enhancement for Perovskite X-ray Detectors.

Organic-inorganic hybrid perovskites have been recognized as potential candidates in direct X-ray detectors and have triggered tremendous interest in the past years. The blade coating method meets the requirements of large area and low cost for perovskite X-ray detectors, while the low compactness resulting from solvent evaporation limits the charge collection efficiency (CCE) and device sensitivity. Most of the reports are focused on the melioration of perovskite films to increase device sensitivity; there are still problems of low CCE. Herein, we introduce an intercalation-electrode device structure and achieve a ∼20-fold sensitivity enhancement. Carrier distribution throughout the thick films is simulated, and the electrode intercalating site can be optimized according to the mobility-lifetime factor to achieve the highest CCE. A methylamine thiocyanate (MASCN) additive-assisted coating strategy is developed, and pinhole free thick films with regrown particles are obtained without frequently used hot/soft pressing. A sensitivity level of ∼105 μC Gyair-1 cm-2 as well as a detection limit of 77 nGyair s-1 is achieved under low bias, which is among the best performance for polycrystalline perovskite direct X-ray detectors. This work provides a universal device structure design to overcome carrier loss through a long transport distance and enhances the CCE for ultrahigh sensitivity.