Vapor-Induced Assembly of a Platinum(II) Complex Loaded on Layered Double Hydroxide Nanoparticles.

Controlled self-assembly of PtII complexes is key to the development of optical and stimuli-responsive materials, but designing and precisely controlling them is still difficult owing to weak intermolecular interactions. Herein, we report the successful water-vapor-induced assembly of an anionic PtII complex [Pt(CN)2 (ppy)]- (Hppy=2-phenylpyridine) electrostatically loaded onto cationically charged layered double hydroxide (LDH) nanoparticles consisting of Mg2+ and Al3+ ions. When the PtII complexes were densely loaded onto the LDH nanoparticles, the assembly was maintained, even in dilute aqueous media. In the case of sparse loading, the PtII complexes were loaded discretely in the dry state; however, when water vapor was adsorbed, the increased mobility of the PtII complexes led to their assembly on the LDH nanoparticles. The presence of water vapor led to a drastic change in luminescence from green to orange.

Vapor-Induced Assembly of a Platinum(II) Complex Loaded on Layered Double Hydroxide Nanoparticles.

Invited for the cover of this issue is the group of Masaki Yoshida and Masako Kato at Hokkaido University/Kwansei Gakuin University. The image depicts the changes in the assembly of PtII complexes with humidity on layered double hydroxide (LDH) nanoparticles, resulting in a drastic emission color change from green to orange. Read the full text of the article at 10.1002/chem.202301993.

Intense Red-Blue Luminescence Based on Superfine Control of Metal-Metal Interactions for Self-Assembled Platinum(II) Complexes.

A series of assembled PtII complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups, [Pt(CN)2 (R-impy)] (R-impyH+ =1-alkyl-3-(2-pyridyl)-1H-imidazolium, R=Me (Pt-Me), Et (Pt-Et), i Pr (Pt-i Pr), and t Bu (Pt-t Bu)). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield of 0.51-0.81 in the solid state at room temperature, originating from the triplet metal-metal-to-ligand charge transfer (3 MMLCT) state. Their emission colors cover the entire visible region from red for Pt-Me to blue for Pt-t Bu. Importantly, Pt-t Bu is the first example that exhibits blue 3 MMLCT emission. The 3 MMLCT emission was proved and characterized based on the temperature dependences of the crystal structures and emission properties. The wide-range color tuning of luminescence using the 3 MMLCT emission presents a new strategy of superfine control of the emission color.

Nanometer scale fabrication and optical response of InGaN/GaN quantum disks.

In this work, we demonstrate homogeneously distributed In0.3Ga0.7N/GaN quantum disks (QDs), with an average diameter below 10 nm and a high density of 2.1 × 10(11) cm(-2), embedded in 20 nm tall nanopillars. The scalable top-down fabrication process involves the use of self-assembled ferritin bio-templates as the etch mask, spin coated on top of a strained In0.3Ga0.7N/GaN single quantum well (SQW) structure, followed by a neutral beam etch (NBE) method. The small dimensions of the iron cores inside ferritin and nearly damage-free process enabled by the NBE jointly contribute to the observation of photoluminescence (PL) from strain-relaxed In0.3Ga0.7N/GaN QDs at 6 K. The large blueshift of the peak wavelength by over 70 nm manifests a strong reduction of the quantum-confined Stark effect (QCSE) within the QD structure, which also agrees well with the theoretical prediction using a 3D Schrödinger equation solver. The current results hence pave the way towards the realization of large-scale III-N quantum structures using the combination of bio-templates and NBE, which is vital for the development of next-generation lighting and communication devices.

Photophysical properties and biocompatibility of Photoluminescent Y2O3:Eu nanoparticles in polymethylmetacrylate matrix.

In this study, we produced europium-doped yttoria (Y2O3:Eu) nanoparticles and investigated their photoluminescent properties and biocompatibility. The Y2O3:Eu nanoparticles showed excellent photoluminescent properties and cytocompatibility. We also analyzed the photophysical properties of the nanoparticles in PMMA films. When the Y2O3:Eu nanoparticles were incorporated in the polymer film, they showed a strong red emission spectrum, similar to that seen with the particles alone. Energy dispersive X-ray spectroscopy (EDS) measurements indicated that the particles were distributed homogeneously in the PMMA film. Such materials could be applied not only to optoelectronic devices but also to biomedical applications such as bioimaging tools or luminescent medical/dental adhesive materials.

Thermo-responsive emission induced by different delocalized excited-states in isomorphous Pd(ii) and Pt(ii) one-dimensional chains.

The self-assembly of d8 transition metal complexes is essential for the development of optoelectronic and sensing materials with superior photofunctional properties. However, detailed insight into the electronic delocalization of excited states across multiple molecules, particularly in comparing 5d8 (Pt(ii)) and 4d8 (Pd(ii)) systems, remains ambiguous but important. In this study, we have successfully evaluated the differences in the excited-state delocalization and thermal responses of self-assembled Pt(ii) and Pd(ii) complexes. Although the complexes presented herein, K[M(CN)2(dFppy)]·H2O (M = Pt or Pd, dFppy = 2-(4,6-difluorophenyl)pyridinate), are crystallographically isomorphous with similarly short metal⋯metal contacts, only the Pt(ii) complex exhibited thermal equilibria between delocalized excited states, resulting in a drastic thermochromic luminescence with a red-shift of greater than 100 nm. In contrast, the dimeric localized emission from the Pd(ii) complex showed a significant increase in the quantum yield upon cooling, approaching almost unity.

Quantum size effects in GaAs nanodisks fabricated using a combination of the bio-template technique and neutral beam etching.

We successfully fabricated defect-free, distributed and sub-20-nm GaAs quantum dots (named GaAs nanodisks (NDs)) by using a novel top-down technique that combines a new bio-template (PEGylated ferritin) and defect-free neutral beam etching (NBE). Greater flexibility was achieved when engineering the quantum levels of ND structures resulted in greater flexibility than that for a conventional quantum dot structure because structures enabled independent control of thickness and diameter parameters. The ND height was controlled by adjusting the deposition thickness, while the ND diameter was controlled by adjusting the hydrogen-radical treatment conditions prior to NBE. Photoluminescence emission due to carrier recombination between the ground states of GaAs NDs was observed, which showed that the emission energy shift depended on the ND diameters. Quantum level engineering due to both diameter and thickness was verified from the good agreement between the PL emission energy and the calculated quantum confinement energy.

Room-temperature electric field control of spin filtering efficiency for enhanced modulation of optical spin polarization in a defect-functional 0D-2D hybrid nanostructure.

In order to accomplish spin-based photoelectric information processing, it is necessary to modulate electron spin polarization in III-V semiconductor quantum dots (QDs) using an electric field. However, there is a principal limitation to the spin polarization degree and its control range, as the electron spin polarization is rapidly lost during injection into the QDs at room temperature (RT). Here, electric field control of optical spin polarization in the range of 15-40% is demonstrated at RT using InAs QDs tunnel-coupled with a defect-functional GaNAs quantum well (QW) spin filter. This compares with an electric field control of 1-4% for InAs QDs tunnel-coupled with an InGaAs QW. Transient polarization in the range of 30-60% is also obtained in the ultrafast time domain of less than 100 ps, the degree of polarization depending on the electric field. The enhanced polarization control is achieved by tuning the amplified spin polarization of electrons tunnel-injected from the GaNAs QW into QDs via the electric-field-dependent spin-filtering efficiency of GaNAs. These findings will provide a new way to extensively modulate the electron spin polarization in opto-semiconductors, by electric-field-induced on/off switching of spin amplification.

Wafer-scale integration of GaAs/AlGaAs core-shell nanowires on silicon by the single process of self-catalyzed molecular beam epitaxy.

GaAs/AlGaAs core-shell nanowires, typically having 250 nm diameter and 6 µm length, were grown on 2-inch Si wafers by the single process of molecular beam epitaxy using constituent Ga-induced self-catalysed vapor-liquid-solid growth. The growth was carried out without specific pre-treatment such as film deposition, patterning, and etching. The outermost Al-rich AlGaAs shells form a native oxide surface protection layer, which provides efficient passivation with elongated carrier lifetime. The 2-inch Si substrate sample exhibits a dark-colored feature due to the light absorption of the nanowires where the reflectance in the visible wavelengths is less than 2%. Homogeneous and optically luminescent and adsorptive GaAs-related core-shell nanowires were prepared over the wafer, showing the prospect for large-volume III-V heterostructure devices available with this approach as complementary device technologies for integration with silicon.

Control of optical bandgap energy and optical absorption coefficient by geometric parameters in sub-10 nm silicon-nanodisc array structure.

A sub-10 nm, high-density, periodic silicon-nanodisc (Si-ND) array has been fabricated using a new top-down process, which involves a 2D array bio-template etching mask made of Listeria-Dps with a 4.5 nm diameter iron oxide core and damage-free neutral-beam etching (Si-ND diameter: 6.4 nm). An Si-ND array with an SiO(2) matrix demonstrated more controllable optical bandgap energy due to the fine tunability of the Si-ND thickness and diameter. Unlike the case of shrinking Si-ND thickness, the case of shrinking Si-ND diameter simultaneously increased the optical absorption coefficient and the optical bandgap energy. The optical absorption coefficient became higher due to the decrease in the center-to-center distance of NDs to enhance wavefunction coupling. This means that our 6 nm diameter Si-ND structure can satisfy the strict requirements of optical bandgap energy control and high absorption coefficient for achieving realistic Si quantum dot solar cells.

Sub-picosecond spin relaxation of bright excitons and imbalance suppression in asymmetric Cdse/Zns nanocrystal quantum dots under an applied magnetic field.

The ultrafast spin dynamics of the bright exciton in CdSe/ZnS nanocrystal quantum dots has been investigated using a circularly polarized pump-probe experiment. A remarkably fast spin flip (-500 fs) of the bright exciton was observed at 4 K, which is attributed to the anisotropic electron-hole exchange interaction and the random positioning of nanocrystal quantum dots. In the presence of an applied magnetic field (5 T), the exciton spin parallel to the external magnetic field was favored due to Zeeman splitting. We found that this imbalance can possibly be suppressed by the state-blocking and the mixing of the 1(L) and 1(U) states in asymmetric quantum dots.

Optical absorption characteristic of highly ordered and dense two-dimensional array of silicon nanodiscs.

We created a two-dimensional array of sub-10 nm Si-nanodiscs (Si-NDs), i.e. a 2D array of Si-NDs, with a highly ordered arrangement and dense NDs by using a new top-down technique comprising advanced damage-free neutral-beam (NB) etching and a bio-template (iron oxide core) as a uniform sub-10 nm etching mask. The bandgap energy (E(g)) of the fabricated 2D array of Si-NDs can be simply controlled from 2.2 to 1.3 eV by changing the ND thickness from 2 to 12 nm. Due to weak quantum confinement existing in the diameter direction resulting from the sub-10 nm Si-ND diameter, even though the thickness of the Si-ND is much larger than the Bohr radius of Si, E(g) is still larger than the 1.1 eV E(g) of bulk Si. Si-ND not only has wide controllable E(g) but also a high absorption coefficient due to quantum confinement in three dimensions. This new technique is a promising candidate for developing new nanostructures and could be integrated into the fabrication of nanoelectronic devices.

Electric-Field-Effect Spin Switching with an Enhanced Number of Highly Polarized Electron and Photon Spins Using p-Doped Semiconductor Quantum Dots.

Electric-field-effect spin switching with an enhanced number of highly polarized electron and photon spins has been demonstrated using p-doped semiconductor quantum dots (QDs). Remote p-doping in InGaAs QDs tunnel-coupled with an InGaAs quantum well (QW) significantly increased the circularly polarized, thus electron-spin-polarized, photoluminescence intensity, depending on the electric-field-induced electron spin injection from the QW as a spin reservoir into the QDs. The spin polarity and polarization degree during this spin injection can be controlled by the direction and the strength of the electric field, where the spin direction can be reversed by excess electron spin injection into the QDs via spin scattering at the QD excited states. We found that the maximum degrees of both parallel and antiparallel spin polarization to the initial spin direction in the QW can be enhanced by p-doping. The doped holes without spin polarization can effectively contribute to this electric-field-effect spin switching after the initial electron spin injection selectively removes the parallel hole spins. The optimized p-doping induces fast spin reversals at the QD excited states with a moderate electric-field application, resulting in an efficient electric-field-driven antiparallel spin injection into the QD ground state. Further excess hole doping prevents this efficient spin reversal due to multiple electron-hole spin scattering, in addition to a spin-state filling effect at the QD excited states, during the spin injection from the QW into the QDs.

[A case of recurrence of breast cancer 36 years after mastectomy treated with endocrine and chemotherapy].

In 2001, a 72-year-old woman, who had undergone left mastectomy for breast carcinoma 36 years ago, was admitted because of dysphagia. Chest CT showed pleural effusion in the right side and no tumor in the breast. Chest drainage was performed. Cytology of chest effusion revealed adenocarcinoma. A high serum CA15-3 level was noted. She was diagnosed with a pleural recurrence of breast cancer, so administration of CAF agents (4 courses) was started. Pleural effusion was improved and the serum CA15-3 level was reduced. She was then clinically followed on medication with oral anastrozole (AI). After 4 years, progression of disease was noted. The serum CA15-3 level was elevated. A tumor measuring 3 cm was confirmed on the right chest wall. The tumor was removed under local anesthesia and pathological findings showed invasive ductal carcinoma expressing estrogen receptor. Chemotherapy with taxane had to be withdrawn because of its side effect. Administration of S-1 was then started. The serum CA15-3 level was gradually elevated. Thereafter, the regimen was switched to combined S-1 and toremifene citrate. The serum CA15-3 level was reduced and sustained for several months. However, she died of multiple organ metastasis in 2008.

[Chemotherapy-naïve advanced malignant fibrohistiocytoma presenting IVC syndrome case report].

The case was a 77-year-old male with swelling of his right leg. Physical examination revealed an ill-defined mass at RLQ. Computed tomography (CT) and 3 dimensional CT showed an 8-cm tumor on the IVC, partially replacing iliac vessels and invading the psoas muscle. A diagnosis of malignant fibrohistiocytoma was made by pathological examination of biopsied specimens at exploratory laparotomy. Five courses of combination chemotherapy of ifosfamide (IFM) and doxorubicin (DXR) resulted in PR. Edema of the lower leg and hydronephrosis were both alleviated. Another 5 courses of chemotherapy with epirubicin and IFM were added. PR lasted 2 years, though the patient succumbed to the disease in 2 years and 8 months.

[A case of small cell carcinoma of the esophagus with SIADH].

The patient was a 63-year-old male admitted for further evaluation of the bleeding esophageal tumor. Endoscopic biopsy revealed small cell carcinoma. CT scan of the abdomen demonstrated nodular enlargement at the celiac axis. Under diagnosis of small cell carcinoma of the esophagus at Stage IVa, neoadjuvant chemotherapy with FP (5-FU+CDDP) was given. Immediately after fluid load, levels of serum sodium decreased to 117 mEq/L and persisted during chemotherapy treatment despite aggressive corrections. Response and shrinkage of the distant nodal metastases were confirmed, and an esophagectomy was conducted. Pathological examination with IHC demonstrated positive staining for CD56, NSE and synaptophysin but negative for ADH. Lymph node and liver metastases recurred. Progression of the disease again triggered hyponatremia.

Light-emitting devices based on top-down fabricated GaAs quantum nanodisks.

Quantum dots photonic devices based on the III-V compound semiconductor technology offer low power consumption, temperature stability, and high-speed modulation. We fabricated GaAs nanodisks (NDs) of sub-20-nm diameters by a top-down process using a biotemplate and neutral beam etching (NBE). The GaAs NDs were embedded in an AlGaAs barrier regrown by metalorganic vapor phase epitaxy (MOVPE). The temperature dependence of photoluminescence emission energies and the transient behavior were strongly affected by the quantum confinement effects of the embedded NDs. Therefore, the quantum levels of the NDs may be tuned by controlling their dimensions. We combined NBE and MOVPE in a high-throughput process compatible with industrial production systems to produce GaAs NDs with tunable optical characteristics. ND light emitting diode exhibited a narrow spectral width of 38 nm of high-intensity emission as a result of small deviation of ND sizes and superior crystallographic quality of the etched GaAs/AlGaAs layer.

Temperature dependence of time-resolved photoluminescence in closely packed alignment of Si nanodisks with SiC barriers.

We study the temperature dependence of time-resolved photoluminescence (PL) in closely packed alignment of Si nanodisks (NDs) with SiC barriers, fabricated by neutral beam etching using bio-nano-templates. The PL time profile indicates three decaying components with different decay times. The PL intensities in the two slower decaying components depend strongly on temperature. These temperature dependences of the PL intensity can be quantitatively explained by a three-level model with thermal activation energies of 410 and 490 meV, depending on the PL components. The activation energies explain PL quenching due to thermal escape of electrons from individual NDs. This thermal escape affects the PL decay times above 250 K. Dark states of photo-excited carriers originating from the separate localization of electron and hole into different NDs are elucidated with the localization energies of 70 and 90 meV. In contrast, the dynamics of the fastest PL decaying component is dominated by electron tunneling among NDs, where the PL intensity and decay time are constant for temperature.

Picosecond carrier dynamics induced by coupling of wavefunctions in a Si-nanodisk array fabricated by neutral beam etching using bio-nano-templates.

The picosecond carrier dynamics in a closely packed Si-nanodisk (Si-ND) array with ultrathin potential barrier fabricated by neutral beam etching using bio-nano-templates was investigated by time-resolved photoluminescence (PL). The PL decay curves were analyzed as a function of photon energy by the global fitting method. We show three spectral components with different decay times, where the systematic energy differences of the spectral peaks are clarified: 2.03 eV for the fastest decaying component with a decay time τ = 40 ps, 2.02 eV for τ = 300 ps, and 2.00 eV for τ = 1.6 ns. These energy separations ranging from 10 to 30 meV among the emissive states can be attributed to the coupling of wavefunctions of carriers between neighboring NDs.

Plasmonic enhancements of photoluminescence in hybrid Si nanostructures with Au fabricated by fully top-down lithography.

The authors study plasmonic enhancements of photoluminescence (PL) in Si nanodisk (ND) arrays hybridized with nanostructures such as nanoplates of Au, where these hybrid nanostructures are fabricated by fully top-down lithography: neutral-beam etching using bio-nano-templates and high-resolution electron-beam lithography. The separation distance between the Si ND and Au nanostructure surfaces is precisely controlled by inserting a thin SiO2 layer with a thickness of 3 nm. We observe that PL intensities in the Si NDs are enhanced by factors up to 5 depending on the wavelength by integrating with the Au nanoplates. These enhancements also depend on the size and shape of the Au nanoplates.