Tuning Of Energies Research Articles

Controlled Anisotropic Wetting by Plasma Treatment for Directed Self-Assembly of High-χ Block Copolymers.

The directed self-assembly (DSA) of block copolymers (BCPs) is a promising next-generation lithography technique for high-resolution patterning. However, achieving lithographically applicable BCP organization such as out-of-plane lamellae requires proper tuning of interfacial energies between the BCP domains and the substrate, which remains difficult to address effectively and efficiently with high-χ BCPs. Here, we present the successful generation of anisotropic wetting by plasma treatment on patterned spin-on-carbon (SOC) substrates and its application to the DSA of a high-χ Si-containing material, poly(1,1-dimethylsilacyclobutane)-block-polystyrene (PDMSB-b-PS), with a 9 nm half pitch. Exposing the SOC substrate to different plasma chemistries promotes the vertical alignment of the PDMSB-b-PS lamellae within the trenches. In particular, a patterned substrate treated with HBr/O2 plasma gives both a neutral wetting at the bottom interface and a strong PS-affine wetting at the sidewalls of the SOC trenches to efficiently guide the vertical BCP lamellae. Furthermore, prolonged exposure to HBr/O2 plasma enables an adjustment of the trench width and an increased density of BCP lines on the substrate. Experimental observations are in agreement with a free energy configurational model developed to describe the system. These advances, which could be easily implemented in industry, could contribute to the wider adoption of self-assembly techniques in microelectronics, and beyond to applications such as metasurfaces, surface-enhanced Raman spectroscopy, and sensing technologies.

Local tuning of Rydberg exciton energies in nanofabricated Cu2O pillars

Rydberg excitons in Cu2O feature giant optical nonlinearities. To exploit these nonlinearities for quantum applications, the confinement must match the Rydberg blockade size, which in Cu2O could be as large as a few microns. Here, in a top-down approach, we show how exciton confinement can be realised by focused-ion-beam etching of a polished bulk Cu2O crystal without noticeable degradation of the excitonic properties. The etching of the crystal to micron sizes allows for tuning the energies of Rydberg excitons locally, and precisely, by optically induced temperature change. These results pave the way for exploiting the large nonlinearities of Rydberg excitons in micropillars for making non-classical light sources, while the precise tuning of their emission energy opens up a viable pathway for realising a scalable photonic quantum simulation platform.

Single and dual-atom catalysts towards electrosynthesis of ammonia and urea: a review.

Ammonia and urea represent two important chemicals that have contributed to the rapid development of humanity. However, their industrial production requires harsh conditions, consuming excessive energy and resulting in significant greenhouse gas emission. Therefore, there is growing interest in the electrocatalytic synthesis of ammonia and urea as it can be carried out under ambient conditions. Recently, atomic catalysts (ACs) have gained increased attention for their superior catalytic properties, being able to outperform their micro and nano counterparts. This review examines the advantages and disadvantages of ACs and summarises the advancement of ACs in the electrocatalytic synthesis of ammonia and urea. The focus is on two types of AC - single-atom catalysts (SACs) and diatom catalysts (DACs). SACs offer various advantages, including the 100% atom utilization that allows for low material mass loading, suppression of competitive reactions such as hydrogen evolution reaction (HER), and alternative reaction pathways allowing for efficient synthesis of ammonia and urea. DACs inherit these advantages, possessing further benefits of synergistic effects between the two catalytic centers at close proximity, particularly matching the NN bond for N2 reduction and boosting C-N coupling for urea synthesis. DACs also possess the ability to break the linear scaling relation of adsorption energy of reactants and intermediates, allowing for tuning of intermediate adsorption energies. Finally, possible future research directions using ACs are proposed.

Higher-order topological corner states induced solely by on-site potentials with mirror symmetry

Higher-order topological insulators have triggered a great deal of interest because they exhibit nontrivial bulk topology on lower-dimensional boundaries such as corners and hinges. While such interesting phases have been investigated in a plethora of systems by tuning staggered tunneling strength or manipulating existing topological phases, here we show that a higher-order topological phase can be driven solely by mirror-symmetric on-site potentials. We start with a chain model, and we show that it has nonzero edge states due to the lack of internal symmetries such as chiral and particle-hole symmetries. We then generalize the model to two dimensions, and we demonstrate the emergence of topological corner modes. These corner modes are an intrinsic manifestation of nontrivial bulk band topology protected by mirror symmetry, and thus they are robust against symmetry-preserved perturbations. Our model only requires the tuning of on-site energies, and it provides a realistic platform for studying a class of higher-order topological insulators using state-of-the-art experiment techniques.

Independent Tuning of Exciton and Photon Energies in an Exciton–Polariton Condensate by Proton Implantation‐Induced Interdiffusion

AbstractThe use of high energy proton implantation is demonstrated to precisely and independently shift the energies of both exciton and photon components of GaAs microcavity exciton–polaritons. The technique applies post‐growth proton implantation and annealing steps in order to create a small local interdiffusion across either the quantum well–barrier material interfaces, or between the layers of the cavity distributed Bragg reflector mirrors to induce energy shifts to the exciton or photon components, respectively. The polariton mode is tunable by an energy exceeding 10 meV with a corresponding increase (decrease) in effective mass for photon (exciton) energy shifts, while maintaining narrow‐linewidth polariton photoemission and condensation for both photonic and excitonic polaritons. This technique uniquely enables new opportunities to explore coherent polariton matter with narrow‐linewidth and heavy masses in tight‐binding, non‐Hermitian, and topological landscapes with sub‐µm feature‐sizes, while also being a simple post‐growth process.

Electron-Transport Layers Employing Strongly Bound Ligands Enhance Stability in Colloidal Quantum Dot Infrared Photodetectors.

Solution-processed photodetectors based on colloidal quantum dots (CQDs) are promising candidates for short-wavelength infrared light sensing applications. Present-day CQD photodetectors employ a CQD active layer sandwiched between carrier-transport layers in which the electron-transport layer (ETL) is composed of metal oxides. Herein, a new class of ETLs is developed using n-type CQDs, finding that these benefit from quantum-size effect tuning of the band energies, as well as from surface ligand engineering. Photodetectors operating at 1450 nm are demonstrated using CQDs with tailored functionalities for each of the transport layers and the active layer. By optimizing the band alignment between the ETL and the active layer, CQD photodetectors that combine a low dark current of ≈1 × 10-3 mA cm-2 with a high external quantum efficiency of ≈66% at 1V are reported, outperforming prior reports of CQD photodetectors operating at >1400 nm that rely on metal oxides as ETLs. It is shown that stable CQD photodetectors rely on well-passivated CQDs: for ETL CQDs, a strongly bound organic ligand trans-4-(trifluoromethyl)cinnamic acid (TFCA) provides improved passivation compared to the weakly bound inorganic ligand tetrabutylammonium iodide (TBAI). TFCA suppresses bias-induced ion migration inside the ETL and improves the operating stability of photodetectors by 50× compared to TBAI.

Tuning Exciton Coupling of Merocyanine Nucleoside Dimers by RNA, DNA and GNA Double Helix Conformations.

Exciton coupling between two or more chromophores in a specific environment is a key mechanism associated with color tuning and modulation of absorption energies. This concept is well exemplified by natural photosynthetic proteins, and can also be achieved in synthetic nucleic acid nanostructures. Here we report the coupling of barbituric acid merocyanine (BAM) nucleoside analogues and show that exciton coupling can be tuned by the double helix conformation. BAM is a nucleobase mimic that was incorporated in the phosphodiester backbone of RNA, DNA and GNA oligonucleotides. Duplexes with different backbone constitutions and geometries afforded different mutual dye arrangements, leading to distinct optical signatures due to competing modes of chromophore organization via electrostatic, dipolar, π–π‐stacking and hydrogen‐bonding interactions. The realized supramolecular motifs include hydrogen‐bonded BAM–adenine base pairs and antiparallel as well as rotationally stacked BAM dimer aggregates with distinct absorption, CD and fluorescence properties.

Tuning Exciton Coupling of Merocyanine Nucleoside Dimers by RNA, DNA and GNA Double Helix Conformations

AbstractExciton coupling between two or more chromophores in a specific environment is a key mechanism associated with color tuning and modulation of absorption energies. This concept is well exemplified by natural photosynthetic proteins, and can also be achieved in synthetic nucleic acid nanostructures. Here we report the coupling of barbituric acid merocyanine (BAM) nucleoside analogues and show that exciton coupling can be tuned by the double helix conformation. BAM is a nucleobase mimic that was incorporated in the phosphodiester backbone of RNA, DNA and GNA oligonucleotides. Duplexes with different backbone constitutions and geometries afforded different mutual dye arrangements, leading to distinct optical signatures due to competing modes of chromophore organization via electrostatic, dipolar, π–π‐stacking and hydrogen‐bonding interactions. The realized supramolecular motifs include hydrogen‐bonded BAM–adenine base pairs and antiparallel as well as rotationally stacked BAM dimer aggregates with distinct absorption, CD and fluorescence properties.

Effects of single quantum rotational excitation on reaction of F+D2 at collision energies between 44 and 164 cm−1

There is no general picture to describe the influences of reagent rotational excitation on the reaction, which proceeds via the tunnelling mechanism at collision energies far below the reaction barrier. Here we report a crossed beam study on the prototypical reaction of F + D2(v=0, j=0,1) → DF(v′) + D at collision energies between 44 and 164 cm−1 with the scheme of multichannel D-atom Rydberg tagging time-of-flight detection. Vibrational state resolved differential cross sections are obtained at v′=2, 3, 4 levels. The effects of reagent rotational excitation were investigated at an equivalent amount of total energy by precise tuning of translational energies. Compared with translation, the rotation of D2 is found to be more efficient to promote the title reaction. Profound differences introduced by rotation of D2 are also observed on the angular distribution and quantum state distribution of DF products. We hope the present work could provide an example for understanding the effects of reagent rotational excitation on the chemical reaction at energies that are much lower than the reaction barrier.

A different perspective for nonphotochemical quenching in plant antenna complexes

Light-harvesting complexes of plants exert a dual function of light-harvesting (LH) and photoprotection through processes collectively called nonphotochemical quenching (NPQ). While LH processes are relatively well characterized, those involved in NPQ are less understood. Here, we characterize the quenching mechanisms of CP29, a minor LHC of plants, through the integration of two complementary enhanced-sampling techniques, dimensionality reduction schemes, electronic calculations and the analysis of cryo-EM data in the light of the predicted conformational ensemble. Our study reveals that the switch between LH and quenching state is more complex than previously thought. Several conformations of the lumenal side of the protein occur and differently affect the pigments’ relative geometries and interactions. Moreover, we show that a quenching mechanism localized on a single chlorophyll-carotenoid pair is not sufficient but many chlorophylls are simultaneously involved. In such a diffuse mechanism, short-range interactions between each carotenoid and different chlorophylls combined with a protein-mediated tuning of the carotenoid excitation energies have to be considered in addition to the commonly suggested Coulomb interactions.

Stress-controlled zero-field spin splitting in silicon carbide

We report the influence of static mechanical deformation on the zero-field spin splitting of silicon vacancies in silicon carbide at room temperature. We use AlN/6H-SiC heterostructures deformed by growth conditions and monitor the stress distribution as a function of distance from the heterointerface with spatially resolved confocal Raman spectroscopy. The zero-field spin splitting of the V1/V3 and V2 centers in 6H-SiC, measured by optically detected magnetic resonance, reveals significant changes at the heterointerface compared to the bulk value. This approach allows unambiguous determination of the spin-deformation interaction constant, which is 0.75 GHz/strain for the V1/V3 centers and 0.5 GHz/strain for the V2 centers. Provided piezoelectricity of AlN, our results offer a strategy to realize fine tuning of spin transition energies in SiC by deformation.

Atomic Bonding and Electronic Binding Energy of Two-Dimensional Bi/Li(110) Heterojunctions via BOLS-BB Model.

Combining the bond-order-length-strength (BOLS) and atomic bonding and electronic model (BB model) with density functional theory (DFT) calculations, we studied the atomic bonding and electronic binding energy behavior of Bi atoms adsorbed on the Li(110) surface. We found that the Bi atoms adsorbed on the Li(110) surface form two-dimensional (2D) geometric structures, including letter-, hexagon-, galaxy-, crown-, field-, and cobweb-shaped structures. Thus, we obtained the following quantitative information: (i) the field-shaped structure can be considered the bulk structure; (ii) the field-shaped structure of Bi atom formation has a 5d energy level of 22.727 eV, and in the letter shape structure, this energy is shifted to values greater than 0.342 eV; and (iii) the Bi/Li(110) heterojunction transfers charge from the inner Li atomic layer to the outermost Bi atomic layer. In addition, we analyzed the bonding and electronic dynamics involved in the formation of the Bi/Li(110) heterojunctions using residual density of states. This work provides a theoretical reference for the fine tuning of binding energies and chemical bonding at the interfaces of 2D metallic materials.

Electronic modulation of oxygen evolution on metal doped NiFe layered double hydroxides

The bottleneck of electrochemical water splitting is the sluggish kinetics of oxygen evolution reaction (OER). Layered double hydroxides (LDHs) have been proposed as active and affordable electrocatalysts in OER. It has been reported that the activity of LDHs can be effectively tuned by doping of other metals. Despite previous experimental synthesis and improved catalytic performance, the in-depth OER mechanism on metal doped LDHs remains ambiguous. In the present work, transition metals (Cr, Mn and Co) doped NiFe LDHs were designed to investigate the doping effect in OER by both experimental analysis and density functional theory calculations. Based on experimental results, the intrinsic OER activity is Cr-NiFe LDHs > Co-NiFe LDHs > Mn-NiFe LDHs > NiFe LDHs, while the enhanced catalytic performance upon doping can be attributed to the interface effect, which results in the tuning of the binding energies of the intermediate states in OER.

Electrochemical Reduction of CO2 Using Carbon-Based Materials Modified with 3d-Metal Atoms As Electrocatalysts

For the reductive CO2 fixation using solar energy, photo-generated electrons and/or holes must be captured and utilized for chemical reactions that generate products beneficial to humans. To construct the artificial photosynthesis systems, electron transfer catalysts designed to promote electrochemical CO2 reduction reactions (CO2RR) are a critical requirement. Previous studies have shown that precise tuning of adsorption energies of key intermediates is critical for obtaining high activity and reaction selectivity. There are two important factors that determine the adsorption energy of the intermediate on electrocatalysts. First, the metal species in the catalyst, i.e., the transition metals at the active sites with a higher number of d-electrons, tend to reduce the adsorption energy. Previous works have investigated the effects of metal species on the CO2RR using organometallic complexes as platforms to support various metals via coordination bonds. For example, cobalt-modified tetraphenylporphyrin (TPP) is known to exhibit efficient CO2RR activity due to its proper binding strength to COOH*, whereas nickel (Ni) and copper (Cu) modified TPP are known to have low catalytic activity due to the low binding energy of COOH*. The second critical factor is the coordination structure of the metal. First-principles calculations have revealed that a decrease in the coordination number of Pt and Cu in the bulk increases the bond strength of CO* and affects the activity of the CO2RR. Thus, it can be expected that the coordination number can be a control parameter to improve the performance of metal species that were previously thought to have no CO2RR activity. We have investigated the effects of metal species and the coordination structure on CO2RR using graphene and covalent triazine frameworks (CTF)[1,2]. CTF consisting of microporous conjugated polymers with 1,3,5-triazine linker units, are suitable for investigating the above issue due to the high design flexibility. Through the studies, we have revealed that Ni-modified graphene and CTF can work as efficient electrocatalysts for CO2RR due to the unsaturation nature of the Ni atoms on the substrate. In this talk, we report our systematic studies on CO2RR using carbon-based materials with 3d metal atoms, focusing on the effects of metal species and coordination structures.[1] P. Su, K. Iwase, S. Nakanishi, K. Hashimoto, K. Kamiya, Small, 12, 6083-6089 (2016).[2] P. Su, K. Iwase, T. Harada, K. Kamiya, S. Nakanishi, Chem. Sci., 9, 3941-3947 (2018). Figure 1

Framework for simulating gauge theories with dipolar spin systems

Gauge theories appear broadly in physics, ranging from the standard model of particle physics to long-wavelength descriptions of topological systems in condensed matter. However, systems with sign problems are largely inaccessible to classical computations and also beyond the current limitations of digital quantum hardware. In this work, we develop an analog approach to simulating gauge theories with an experimental setup that employs dipolar spins (molecules or Rydberg atoms). We consider molecules fixed in space and interacting through dipole-dipole interactions, avoiding the need for itinerant degrees of freedom. Each molecule represents either a site or gauge degree of freedom, and Gauss law is preserved by a direct and programmatic tuning of positions and internal state energies. This approach can be regarded as a form of analog systems programming and charts a path forward for near-term quantum simulation. As a first step, we numerically validate this scheme in a small-system study of U(1) quantum link models in (1+1) dimensions with link spin S = 1/2 and S = 1 and illustrate how dynamical phenomena such as string inversion and string breaking could be observed in near-term experiments. Our work brings together methods from atomic and molecular physics, condensed matter physics, high-energy physics, and quantum information science for the study of nonperturbative processes in gauge theories.

Tuning Adsorption Energies and Reaction Pathways by Alloying: PdZn versus Pd for CO2 Hydrogenation to Methanol.

The tunability offered by alloying different elements is useful to design catalysts with greater activity, selectivity, and stability than single metals. By comparing the Pd(111) and PdZn(111) model catalysts for CO2 hydrogenation to methanol, we show that intermetallic alloying is a possible strategy to control the reaction pathway from the tuning of adsorbate binding energies. In comparison to Pd, the strong electron-donor character of PdZn weakens the adsorption of carbon-bound species and strengthens the binding of oxygen-bound species. As a consequence, the first step of CO2 hydrogenation more likely leads to the formate intermediate on PdZn, while the carboxyl intermediate is preferentially formed on Pd. This results in the opening of a pathway from carbon dioxide to methanol on PdZn similar to that previously proposed on Cu. These findings rationalize the superiority of PdZn over Pd for CO2 conversion into methanol and suggest guidance for designing more efficient catalysts by promoting the proper reaction intermediates.

Size and Shape Evolution of GaAsSb-Capped InAs/GaAs Quantum Dots: Dependence on the Sb Content

Capping InAs/GaAs quantum dots (QDs) with a thin GaAsSb layer alters the QDs structural properties, leading to considerable changes in their optical properties. The increase of the Sb content induces a redshift of the emission energies, indicating a change in the buried QDs shape and size. The presence of well-defined ground- and excited-state emission bands in all the photoluminescence spectra allow an accurate estimation of the buried QDs size and shape by numerical evaluation and tuning of the theoretical emission energies. For an Sb content below 14%, the QDs are found to have a type I band alignment with a truncated height pyramidal form. However, for higher Sb content (22%), the QDs are present in a full pyramidal shape. The observed behavior is interpreted in terms of increasing prevention of InAs QDs decomposition with increasing the Sb content in the cap layer.

Trapping and Electron Paramagnetic Resonance Characterization of the 5'dAdo• Radical in a Radical S-Adenosyl Methionine Enzyme Reaction with a Non-Native Substrate.

S-Adenosyl methionine (SAM) is employed as a [4Fe-4S]-bound cofactor in the superfamily of radical SAM (rSAM) enzymes, in which one-electron reduction of the [4Fe-4S]-SAM moiety leads to homolytic cleavage of the S-adenosyl methionine to generate the 5′-deoxyadenosyl radical (5′dAdo•), a potent H-atom abstractor. HydG, a member of this rSAM family, uses the 5′dAdo• radical to lyse its substrate, tyrosine, producing CO and CN that bind to a unique Fe site of a second HydG Fe–S cluster, ultimately producing a mononuclear organometallic Fe-l-cysteine-(CO)2CN complex as an intermediate in the bioassembly of the catalytic H-cluster of [Fe–Fe] hydrogenase. Here we report the use of non-native tyrosine substrate analogues to further probe the initial radical chemistry of HydG. One such non-native substrate is 4-hydroxy phenyl propanoic acid (HPPA) which lacks the amino group of tyrosine, replacing the CαH-NH2 with a CH2 at the C2 position. Electron paramagnetic resonance (EPR) studies show the generation of a strong and relatively stable radical in the HydG reaction with natural abundance and 13C2-HPPA, with appreciable spin density localized at C2. These results led us to try parallel experiments with the more oxidized non-native substrate coumaric acid, which has a C2=C3 alkene substitution relative to HPPA’s single bond. Interestingly, the HydG reaction with the cis-p-coumaric acid isomer led to the trapping of a new radical EPR signal, and EPR studies using cis-p-coumaric acid along with isotopically labeled SAM reveal that we have for the first time trapped and characterized the 5′dAdo• radical in an actual rSAM enzyme reaction, here by using this specific non-native substrate cis-p-coumaric acid. Density functional theory energetics calculations show that the cis-p-coumaric acid has approximately the same C–H bond dissociation free energy as 5′dAdo•, providing a possible explanation for our ability to trap an appreciable fraction of 5′dAdo• in this specific rSAM reaction. The radical’s EPR line shape and its changes with SAM isotopic substitution are nearly identical to those of a 5′dAdo• radical recently generated by cryophotolysis of a prereduced [4Fe-4S]-SAM center in another rSAM enzyme, pyruvate formate-lyase activating enzyme, further supporting our assignment that we have indeed trapped and characterized the 5′dAdo• radical in a radical SAM enzymatic reaction by appropriate tuning of the relative radical free energies via the judicious selection of a non-native substrate.

Tuning of adsorption energies of CO2 and CH4 in borocarbonitrides BxCyNz: A first-principles study

We present density functional theory based calculations with semiempirical dispersion (DFT-D) analysis of CO2, CH4, N2 and H2 adsorption at various sites of 2-dimensional BCN with various chemical ordering of B, C and N and also on graphene and C-BN arm-chair interface of BC2N having graphene and BN domains. We find BCN and BC2N shows greater ability to absorb these gases as compared to graphene. CO2 binds strongly as compared to other gases with optimum storage of 44 wt% for a monolayer of BCN. A significant new result is that when BC2N sheets are doped with boron they show significant increase in adsorption energies for CO2 and CH4. Through the present work, we propose a way to tune adsorption energies of CO2 and CH4 by changing the doping concentration of boron.

(Invited) Organic Molecular Tuning of Many-Body Interaction Energies in Air-Suspended Carbon Nanotubes

Environmental screening effects are large in carbon nanotubes due to their atomically thin nature, and therefore it is possible to control the optical properties with molecular adsorption [1,2]. Here we investigate adsorption effects of copper phthalocyanine molecules on excitons and trions in air-suspended carbon nanotubes [3]. Using photoluminescence excitation spectroscopy, we observe that exciton energy redshifts gradually with the molecular deposition thickness. The trion emission is also observed at large deposition amounts, which suggests charge transfer between the phthalocyanine molecules and carbon nanotubes. Analyzing the spectra for individual tubes, we find a correlation between the exciton-trion energy separation and the exciton emission energy, indicating that the many-body interaction energies scale similarly with the molecular dielectric screening. Work supported in part by RIKEN (Incentive Research Projects), JSPS (KAKENHI JP16H05962, JP17H07359), and MEXT (Nanotechnology Platform). We acknowledge the Advanced Manufacturing Support Team at RIKEN for technical assistance. [1] T. Uda, A. Ishii, and Y. K. Kato, ACS Photonics 5, 559 (2018).[2] T. Uda, S. Tanaka, and Y. K. Kato, Appl. Phys. Lett. 113, 121105 (2018).[3] S. Tanaka, K. Otsuka, K. Kimura, A. Ishii, H. Imada, Y. Kim, and Y. K. Kato, arXiv:1812.10245 (2018).