Dimensionality Engineering Research Articles

Toward Strong UV-Vis-NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates.

The precise modulation of the spatial orientations and connection modes of primitives is vital for certain critically important optical functions for nonlinear optical (NLO) materials (specifically, second-harmonic generation (SHG) and optical bandgap); however, we are yet to achieve a sufficient level of control for the designed construction of efficient broadband NLO materials. Exploiting the changes in microscopic polarization that may result from dimensional increase, we propose herein a zero-dimensional (0D)-to-three-dimensional (3D) dimensionality-increase strategy to realize strong broadband SHG responses for the first time. The novel 3D pseudo diamond-like Zn(SCN)2 has been synthesized by removing SHG-inactive [NH4]+ counter cations and H2O molecules that are located between the adjacent discrete [Zn(SCN)4] building blocks within the 0D (NH4)2Zn(SCN)4·3H2O. The 0D-to-3D dimensionality engineering, proceeding from (NH4)2Zn(SCN)4·3H2O to Zn(SCN)2, results in significantly enhanced SHG responses and efficient broadband activity (8 × KH2PO4 @ 1064 nm, 4.18 eV bandgap for the former c.f. 2 × β-BaB2O4 @ 380 nm, 30 × KH2PO4 @ 1064 nm, 2 × KTiOPO4 @ 2100 nm, 4.78 eV bandgap for the latter) from the UV to the NIR regions (SHG@300-1050 nm). Theoretical calculations and crystal structure analyses reveal that the coordination-bond-connected [Zn(SCN)4] building blocks within the diamond-like structure of Zn(SCN)2 are responsible for its giant broadband SHG responses.

Chirality-Mediated 1D-to-2D Phase Transition in Hybrid Lead Halide Perovskites.

Dimensionality engineering plays a pivotal role in optimizing the performance, ensuring long-term stability, and expanding the versatile applications of lead halide perovskites (LHPs). Currently, the manipulation of LHP dimensions primarily occurs during the synthesis stage, a procedure hampered by constraints, including synthetic complexity and irreversibility. This investigation successfully achieved a transition from one-dimensional (1D) to two-dimensional (2D) structures in chiral LHPs by applying hydrostatic pressure. Remarkably, this pressure-induced transition in dimensionality is absent in the racemic analogue due to the staggered arrangement of inorganic chains and the elevated steric hindrance posed by the organic cations. Notably, the hydrogen bonding between organic cations and the inorganic framework adopts a symmetrical arrangement in the racemic system but a helical configuration along the 1D chain direction in the chiral counterparts. This distinct helical arrangement induces a consequential distortion in the inorganic moiety, resulting in the emergence of a spin-polarized Rashba-Dresselhaus texture that explains the chirality's electronic spin origin. Furthermore, both experimental and density functional theory calculation results demonstrate that the 1D-to-2D phase transition in chiral halide perovskites can induce significant modifications in the electronic structures and associated optical emissions. In summary, the findings unveil novel avenues for manipulating optoelectronic properties in chiral perovskites through dimensionality engineering.

Dimensionality Engineering toward Carbon Materials for Electrochemical CO2 Reduction: Progress and Prospect

AbstractCarbon materials are of great significance in state‐of‐the‐art electrochemical CO2 reduction (ECR) as key components such as electrocatalysts, gas diffusion electrodes, and current collectors. Notably, dimensionalities of carbons and related manipulations play vital roles in boosting ECR performance, e.g., mass/charge transfer dynamics, exposure of active sites, reaction space, product's Faradaic efficiency/selectivity, and durability. Here, recent endeavors in dimensionality engineering toward advanced carbon‐based materials for ECR is first summarized, including pure carbons (e.g., carbon nanotube and graphene) and carbon composites, and highlight the dimensionality‐dependent properties toward ECR performance. Various engineering strategies referring to dimensionality modulation and integration have been summarized, e.g., top‐down, bottom‐up, and soft chemical approaches. Design principles of dimensionality‐varied carbons are elaborated, the impacts of dimensionalities of carbons and related surface chemistry (e.g., functional group, wettability, and electronic structure) on ECR kinetics and product‐targeted mechanisms are also scrutinized. Some insights into how the dimensionality manipulation of carbons elevates performance of carbon‐based materials in mass/charge transfer acceleration, ECR kinetics, and product selectivity are provided. At last, a perspective for challenges and future development of dimensionality‐varied carbon materials is discussed. This review aims at providing guidance for customizable construction of carbon materials with dimensionality dependence toward green and energy‐saving electrosynthesis systems.

Dimensionality Engineering of Magnetic Anisotropy from the Anomalous Hall Effect in Synthetic SrRuO3 Crystals.

Magnetic anisotropy in atomically thin correlated heterostructures is essential for exploring quantum magnetic phases for next-generation spintronics. Whereas previous studies have mostly focused on van der Waals systems, here we investigate the impact of dimensionality of epitaxially grown correlated oxides down to the monolayer limit on structural, magnetic, and orbital anisotropies. By designing oxide superlattices with a correlated ferromagnetic SrRuO3 and nonmagnetic SrTiO3 layers, we observed modulated ferromagnetic behavior with the change of the SrRuO3 thickness. Especially, for three-unit-cell-thick layers, we observe a significant 1500% improvement of the coercive field in the anomalous Hall effect, which cannot be solely attributed to the dimensional crossover in ferromagnetism. The atomic-scale heterostructures further reveal the systematic modulation of anisotropy for the lattice structure and orbital hybridization, explaining the enhanced magnetic anisotropy. Our findings provide valuable insights into engineering the anisotropic hybridization of synthetic magnetic crystals, offering a tunable spin order for various applications.

Dimensionality engineering of flower-like bimetallic nanozyme with high peroxidase-activity for naked-eye and on-site detection of acrylamide in thermally processed foods

Acrylamide (AA) is a neurotoxin and carcinogen that formed during the thermal food processing. Conventional quantification techniques are difficult to realize on-site detection of AA. Herein, a flower-like bimetallic FeCu nanozyme (FeCuzyme) sensor and portable platform were developed for naked-eye and on-site detection of AA. The FeCuzyme was successfully prepared and exhibited flower-like structure with 3D catalytic centers. Fe/Cu atoms were considered as active center and ligand frameworks were used as cofactor, resulting in collaborative substrate-binding features and remarkably peroxidase-like activity. During the catalytic process, the 3,3′,5,5′-tetrame-thylbenzidine (TMB) oxidation can be quenched by glutathione (GSH), and then restored after thiolene Michael addition reaction between GSH and AA. Given the “on–off–on” effect for TMB oxidation and high POD-like activity, FeCuzyme sensor exhibited a wide linear relationship from 0.50 to 18.00 ​μM ​(R2 ​= ​0.9987) and high sensitivity (LOD ​= ​0.2360 ​μM) with high stability. The practical application of FeCuzyme sensor was successfully validated by HPLC method. Furthermore, a FeCuzyme portable platform was designed with smartphone/laptop, and which can be used for naked-eye and on-site quantitative determination of AA in real food samples. This research provides a way for rational design of a novel nanozyme-based sensing platform for AA detection.

Development of Quasi-Two-Dimensional Perovskites and Their Application in Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskites have attracted much attention due to their outstanding properties, such as inherent quantum-well structure, strong dielectric and quantum confinement, large exciton binding energy, and high photoluminescence quantum yield. By virtue of these superior merits, quasi-2D perovskites have shown great potential for next-generation light-emitting diodes (LEDs). Herein, this review presents an overview of the basic properties of quasi-2D perovskites and their photoluminescence modulations by large organic cation engineering, monovalent cation engineering, halogen engineering, defect passivation engineering, and dimensionality engineering. Furthermore, the strategies of charge-transport layer optimization, interfacial engineering, light-outcoupling efficiency improvement, and operating stability improvement are summarized for fabricating high-performance quasi-2D perovskite LEDs (PeLEDs). Finally, the challenges and outlook for the future development of quasi-2D PeLEDs are unambiguously proposed.

A Comprehensive Review on Defects-Induced Voltage Losses and Strategies toward Highly Efficient and Stable Perovskite Solar Cells

The power conversion efficiency (PCE) of single-junction perovskite solar cells (PSCs) has reached 26.1% in small-scale devices. However, defects at the bulk, surface, grain boundaries, and interfaces act as non-radiative recombination centers for photogenerated electron-hole pairs, limiting the open-circuit voltage and PCE below the Shockley–Queisser limit. These defect states also induce ion migration towards interfaces and contribute to intrinsic instability in PSCs, reducing the quasi-Fermi level splitting and causing anomalous hysteresis in the device. The influence of defects becomes more prominent in large-area devices, demonstrating much lower PCE than the lab-scale devices. Therefore, commercializing PSCs faces a big challenge in terms of rapid decline in working performance due to these intrinsic structural defects. This paper provides a comprehensive review of recent advances in understanding the nature and the classification of defects, their impact on voltage losses, device parameters, intrinsic stability, and defect quantification and characterization techniques. Novel defect passivation techniques such as compositional engineering, additive engineering, post-treatments, dimensionality engineering, and interlayer engineering are also reviewed, along with the improvements in PCE and stability based on these techniques for both small-area devices and large-area roll-to-roll coated devices.

Dimensionality Engineering of Organic-Inorganic Halide Perovskites for Next-Generation X-Ray Detector.

The next-generation X-ray detectors require novel semiconductors with low material/fabrication cost, excellent X-ray response characteristics, and robust operational stability. The family of organic-inorganic hybrid perovskites (OIHPs) materials comprises a range of crystal configuration (i.e., films, wafers, and single crystals) with tunable chemical composition, structures, and electronic properties, which can perfectly meet the multiple-stringent requirements of high-energy radiation detection, making them emerging as the cutting-edge candidate for next-generation X-ray detectors. From the perspective of molecular dimensionality, the physicochemical and optoelectronic characteristics of OIHPs exhibit dimensionality-dependent behavior, and thus the structural dimensionality is recognized as the key factor that determines the device performance of OIHPs-based X-ray detectors. Nevertheless, the correlation between dimensionality of OIHPs and performance of their X-ray detectors is still short of theoretical guidance, which become a bottleneck that impedes the development of efficient X-ray detectors. In the review, the advanced studies on the dimensionality engineering of OIHPs are critically assessed in X-ray detection application, discussing the current understanding on the "dimensionality-property" relationship of OIHPs and the state-of-the-art progresses on the dimensionality-engineered OIHPs-based X-ray detector, and highlight the open challenges and future outlook of this field.

Dimensionality Engineering of Lead Organic Chalcogenide Semiconductors.

Two-dimensional (2D) metal organic chalcogenides (MOCs) such as silver phenylselenolate (AgSePh) have emerged as a new class of 2D materials due to their unique optical properties. However, these materials typically exhibit large band gaps, and their elemental and structural versatility remain significantly limited. In this work, we synthesize a new family of 2D lead organic chalcogenide (LOC) materials with excellent structural and dimensionality tunability by designing the bonding ability of the organic molecules and the stereochemical activity of the Pb lone pair. The introduction of electron-donating substituents on the benzenethiol ligands results in a series of LOCs that transition from 1D to 2D, featuring reduced band gaps (down to 1.7 eV), broadband emission, and strong electron-phonon coupling. We demonstrated a prototypical single crystal photodetector with 2D LOC that showed the dimensionality engineering on the transport property of LOC semiconductors. This study paves the way for further development of the synthesis and optical properties of novel organic-inorganic hybrid 2D materials.

Stabilizing Metal Halide Perovskites for Solar Fuel Production: Challenges, Solutions, and Future Prospects.

Metal halide perovskites (MHPs) are emerging photocatalyst materials that can enable sustainable solar-to-chemical energy conversion by virtue of their broad absorption spectra, effective separation/transport of photogenerated carriers, and solution processability. Although preliminary studies show the excellent photocatalytic activities of MHPs, their intrinsic structural instability due to the low formation energy and soft ionic nature is an open challenge for their practical applications. This review discusses the latest understanding of the stability issue and strategies to overcome this issue for MHP-based photocatalysis. First, the origin of the instability issue at atomic levels and the design rules for robust structures are analyzed and elucidated. This is then followed by presenting several different material design strategies for stability enhancement, including reaction medium modification, material surface protection, structural dimensionality engineering, and chemical composition engineering. Emphases are placed on understanding the effects of these strategies on photocatalytic stability as well as the possible structure-performance correlation. Finally, the possible future research directions for pursuing stable and efficient MHP photocatalysts in order to accelerate their technological maturity on a practical scale are outlined. With that, it is hoped to provide readers a valuable snapshot of this rapidly developing and exciting field.

Dimensionality Engineering of Single-Atom Nanozyme for Efficient Peroxidase-Mimicking.

In nature, enzymatic reactions occur in well-functioning catalytic pockets, where substrates bind and react by properly arranging the catalytic sites and amino acids in a three-dimensional (3D) space. Single-atom nanozymes (SAzymes) are a new type of nanozymes with active sites similar to those of natural metalloenzymes. However, the catalytic centers in current SAzymes are two-dimensional (2D) architectures and the lack of collaborative substrate-binding features limits their catalytic activity. Herein, we report a dimensionality engineering strategy to convert conventional 2D Fe-N-4 centers into 3D structures by integrating oxidized sulfur functionalities onto the carbon plane. Our results suggest that oxidized sulfur functionalities could serve as binding sites for assisting substrate orientation and facilitating the desorption of H2O, resulting in an outstanding specific activity of up to 119.77 U mg-1, which is 6.8 times higher than that of conventional FeN4C SAzymes. This study paves the way for the rational design of highly active single-atom nanozymes.

A Review on Strategies to Fabricate and Stabilize Phase‐Pure α‐FAPbI3 Perovskite Solar Cells

Formamidinium lead triiodide (FAPbI3) with an optimal bandgap of 1.48 eV and superior thermal stability is regarded as one of the most promising perovskite‐based materials for the application in efficient single‐junction solar cells. However, the metastable properties of FAPbI3 due to phase transition from photoactive α phase into an undesired nonperovskite δ phase in ambient conditions become the major factors limiting its further development. Challenges remain in stabilizing α phase structure and preparing phase‐pure α‐FAPbI3 films for high‐efficiency and stable perovskite solar cells (PSCs) devices. Herein, the recent research progress on the strategies is reviewed to fabricate phase‐pure α‐FAPbI3 perovskite and the advances in their photovoltaic application. The physical parameters affecting the phase instability of intrinsic FAPbI3 are first discussed, followed by various methodologies for regulating phase transition behavior, such as additive engineering, solvent optimization, dimensionality engineering, and fabrication techniques. Finally, the fundamental challenges of preparing efficient α‐FAPbI3 PSCs are discussed, and the perspectives on the further development of high‐quality phase‐pure α‐FAPbI3 for reliable PSCs are proposed.

Dimensionality engineering dependence of vertical magnetization shift and magnetic anisotropy evolution in manganite superlattices

The manganite superlattices consisting of a ferromagnetic La0.7Sr0.3MnO3 (LSMO) metal and a G-type antiferromagnetic SrMnO3 (SMO) insulator have been investigated in this work. Two very intriguing effects have been observed in these LSMO/SMO superlattices. The first one is the coexistence of the robust exchange bias and the evident vertical magnetization shift in the thicker superlattices. The second is the magnetic anisotropy variation from planar to perpendicular with increasing SMO layer thickness. These two novel phenomena have been confirmed by the electric transport anisotropy measurements and the microscopic magnetic domain switching images. Moreover, the X-ray linear dichroism experiments and first-principle calculations have revealed the orbital reconstruction dependence on the SMO layer thickness. It is noteworthy that the vertical magnetization shift and perpendicular magnetic anisotropy are usually observed in intrinsic out-of-plane magnetic easy axis materials such as SrRuO3-based heterostructures. However, the spins within LSMO films preferably orient towards the in-plane direction. Therefore, a new microscopic method for vertical magnetization shift and magnetic anisotropy manipulation has been developed, enabling the discovery of emergent phenomena as well as the control of the magnetic properties.

Structural Dimensionality Dependence of the Band Gap in An+1BnX3n+1 Ruddlesden-Popper Perovskites: A Global Picture.

Dimensionality engineering in An+1BnX3n+1 Ruddlesden-Popper (RP) perovskites has recently emerged as a promising tool for tuning the band gap to improve optoelectronic properties. However, the evolution of the band gap is dependent on the material; distinguishing the effects of different factors is urgently needed to guide the rational design of high-performance materials. Through first-principles calculations, we perform a systematic investigation of RP oxide, chalcogenide, and halide perovskites. The results reveal that in addition to the confinement effect and the change in octahedral rotation motions and/or amplitudes, interfacial rumpling and a change in the A-site cation coordination number also determine the evolution of the band gap. More importantly, we emphasize that the evolution of the band gap in RP perovskites is not dependent on the material family. Instead, the B-site frontier orbital type (s, p, and d) and bandwidth, A-site cation, interfacial rumpling, and structural distortions simultaneously determine the evolution of the band gap. These insights enable a complete and deeper understanding of various experimental observations.

Chain-to-Layer Dimensionality Engineering of Chiral Hybrid Perovskites to Realize Passive Highly Circular-Polarization-Sensitive Photodetection.

Chiral hybrid perovskites (CHPs), aggregating chirality and favorable semiconducting properties in one, have taken a prominent position in direct circularly polarized light detection (CPL). However, passive high circular polarization sensitivity (gres) photodetection in CHPs is still elusive and challenging. Benefitting from efficient control and turning of carrier transport of CHPs by dimensional engineering, here, we unprecedentedly proposed a chain-to-layer dimensionality engineering to realize high-gres passive photodetection. Two novel 2D layered CHPs (R/S-PPA)EAPbBr4 (2R/2S) (PPA = 1-phenylpropylamine, EA = ethylammonium) are successfully synthesized by alloying an EA cation with small steric hindrance into the chained CHPs (R/S-PPA)PbBr3 (1R/1S). Particularly, compared with the neglectable photoresponse in 1R, the obtained 2R by chain-to-layer dimensionality engineering gives rise to an excellent photoconductivity and robust polar photovoltage effect (PPE) with a giant open-circuit voltage of 2.5 V. Furthermore, such PPE promotes realizing an impressive gres in 2R up to 0.42 at zero bias because of the independent separation of photoexcited carriers, which is the highest value among the reported layered chiral perovskites. This work paves the way for the vigorous development of higher dimensional CHPs and will reveal their applications in the field of passive high-gres CPL detection.

Humidity-Controlled Dynamic Engineering of Buckling Dimensionality in MoS2 Thin Films

Dynamic engineering of buckling deformation is of vital importance as it provides multiphase modulation of thin film devices. In particular, dynamic switch of buckles between one-dimensional (1D) and two-dimensional (2D) configurations in a single film system on rigid substrates is intriguing but very challenging. The current approach to changing buckling configuration is mainly achieved by varying the built-in stress at the film-substrate interface, but it is difficult to realize dynamic engineering on rigid substrates. Herein, we report a dynamic engineering of buckling deformation in MoS2 thin films by humidity-tuned interfacial adhesion. With the change of humidity, the MoS2 thin films deform from 1D telephone-cord buckles to 2D web-like buckles due to the hydrophilic nature of both MoS2 and substrate. Such 1D-to-2D evolution of buckles is attributed to the weakened interfacial adhesion of mixed deformation modes induced by humidity, which is verified by finite-element modeling. These buckled films further find potential applications as patterned templates for liquid condensation and sensing units for tactile sensors. Our work not only demonstrates the humidity-controlled dimensionality engineering of buckles in MoS2 thin films but also sheds light on the functional applications of buckled films based on their profile features.

Simultaneous Passivation of Bulk and Interface Defects with Gradient 2D/3D Heterojunction Engineering for Efficient and Stable Perovskite Solar Cells

Minimizing bulk and interfacial nonradiative recombination losses is key to further improving the photovoltaic performance of perovskite solar cells (PSC) but very challenging. Herein, we report a gradient dimensionality engineering to simultaneously passivate the bulk and interface defects of perovskite films. The 2D/3D heterojunction is skillfully constructed by the diffusion of an amphiphilic spacer cation from the interface to the bulk. The 2D/3D heterojunction engineering strategy has achieved multiple functions, including defect passivation, hole extraction improvement, and moisture stability enhancement. The introduction of tertiary butyl at the spacer cation should be responsible for increased film and device moisture stability. The device with 2D/3D heterojunction engineering delivers a promising efficiency of 22.54% with a high voltage of 1.186 V and high fill factor of 0.841, which benefits from significantly suppressed bulk and interfacial nonradiative recombination losses. Moreover, the modified devices demonstrate excellent light, thermal, and moisture stability over 1000 h. This work paves the way for the commercial application of perovskite photovoltaics.

Phase-Pure α-FAPbI3 for Perovskite Solar Cells.

Because of the narrow bandgap and superior thermal stability, FAPbI3 is considered the most promising perovskite material for high-performance single-junction PSCs. Nevertheless, the metastable properties of the photoactive α-FAPbI3 becomes a primary obstacle for the development of FA-based PSCs. The main reasons for the instability of α-FAPbI3 are the rotation disorder of the FA cation and large anisotropic lattice strain, which lead to the high formation energy of α-FAPbI3. In this Perspective, we review various strategies for preparing phase-pure α-FAPbI3, such as engineering, intermediate phase engineering, and dimensionality engineering. These strategies can stabilize α-FAPbI3 by reducing the system energy, regulating the phase transition process and energy barrier, reinforcing the lattice structure, and passivating film defects. In addition, we investigate fundamental challenges of α-FAPbI3 PSCs and propose our perspective on preparing high-quality and high-purity α-FAPbI3.

Gold-Based Double Perovskite-Related Polymorphs: Low Dimensional with an Ultranarrow Bandgap

Lead-free halide double perovskites (LFDPs) arouse great interest as environmentally friendly substitutes to the state-of-the-art lead halide perovskites. However, most halide LFDPs feature large bandgaps that afford weak visible-light absorption. Herein, we synthesized and systemically studied the single-crystallographic, physical–chemical, band structural, and electronic properties of a series of multidimensional Au-based lead-free hybrid polymorphs, [(NH3CH3)2(AuI4)(AuI2)], [(NH2CHNH2)(AuI4)(AuI2)], [NH3(CH2)nNH3][(AuI4)2] (n = 2, 3), [NH3(CH2)nNH3][(AuI4)(I3)] (n = 4, 5, 6), and [NH3(CH2)nNH3]2[(AuI4)(AuI2)(I3)2] (n = 7, 8, 9). Among these two-dimensional (2D) perovskite-related and zero-dimensional nonperovskite polymorphs, we found an abnormal variation of structural dimensionality with increasing the size of A-site cations. These polymorphs displayed ultrabroad absorption ranges (200–1300 nm) and tunable low indirect bandgaps (0.93–1.18 eV). Combined single-crystallography and Hall effect measurements demonstrate that the I3– conduces to the formation of 2D perovskite structures related by connecting with the (AuI4)− sheets and also the charge transport properties. Consequently, [NH3(CH2)5NH3][(AuI4)I3] and [NH3(CH2)8NH3]2[(AuI4)(AuI2)(I3)2] showed high spectroscopic limited maximum efficiencies of 28.4 and 20.5%, respectively, with a film thickness of 500 nm. Our findings bring the Au-based polymorphs to the forefront of study on lead-free low-bandgap perovskites for optoelectronics and reveal the unique rule of dimensionality engineering in such materials.

Strategies for highly efficient and stable cesium lead iodide perovskite photovoltaics: mechanisms and processes

Additive engineering, dimensionality engineering, doping engineering and quantum dot technology can effectively improve the efficiency and stability of the most eye-catching all-inorganic CsPbI3 based PSCs.