Ga Ratio Research Articles

Modulating the chemical environment of Ni2+ for the oxidative dehydrogenation of ethane: The formation of LAS(Al3+/Ga3+)-Ni-OH site

The oxidative dehydrogenation of ethane to ethylene (ODHE) usually suffers from the issues of ethane conversion-ethylene selectivity seesaw. Herein, a series of alumina-supported Ni and Ga catalysts with different molar ratios of Ni to Ga were synthesized by facile impregnation method constructing the Lewis acid site (LAS) strategy to obtain great ethylene selectivity (97 %). The variation of Ni:Ga ratio adjusted the ionic substitution ability, redox ability and acidity, thus regulate the chemical environment of Ni2+ to the formation of LAS(Al3+/Ga3+)-Ni-OH structure, which was proposed to be the active site for selective oxidation of ethane to ethylene, as proved by H2-TPR, ToF-SIMS, quasi in-situ XPS and in-situ FTIR. Moreover, the probable mechanism of ODHE reaction was proposed that C2H6 molecules were mainly adsorbed on LAS sites and activated on Ni-OH site of the catalyst. The pulse test further suggested that O- was mainly associated with the generation of CO2 and Ni(2-n)+ was connected with the production of CH4. It is highlighted that adjusting the Ni-related species and oxygen species on the catalyst surface are crucial to further improve the ethylene selectivity.

Composition-optimized NiGa-LDH on MOF-derived and cobalt-nanoparticles-embedded carbon flakes for enhanced potassium-ion storage

Layered double hydroxides (LDHs), renowned for their distinct nanostructures, efficient ion channels, and high specific capacitance, are promising electrode materials for supercapacitors (SCs). However, commercial applications remain limited due to constraints in the rate capabilities and cycling. The synergistic effects of the composites can be leveraged by pairing LDHs with carbon materials to enhance the conductivity for better SC characteristics. Herein, flaky Zeolitic Imidazolate Framework(ZIF)-67 is deposited on carbon cloth and calcined to produce the MOF-derived composite of carbon nanosheet-embedded nano-cobalt particles (CPEC) on the surface of the carbon cloth. Afterward, NiGa-LDH with a controllable Ni to Ga ratio is synthesized on the CPEC to form a flower-like hierarchical nanostructure NiGa-LDH/CPEC@CC. Co nanoparticles act as nucleation sites for cohesive formation within the carbon cloth framework. Ni2Ga1-LDH/CPEC@CC has the best properties, such as a specific capacitance of 729.6F g−1 at 1 mA cm−2 and 97.3 % capacitance retention at 2 mA cm−2. The asymmetric supercapacitor (ASC) consisting of Ni2Ga1-LDH/CPEC@CC//AC has an excellent energy density of 83.96 Wh kg−1 with a power density of 80 W kg−1. Density-functional theory (DFT) calculations of Ni2Ga1-LDH/CPEC@CC affirm a potassium ion adsorption energy of −2.127 eV and density of state (DOS) near the Fermi level. The study imparts theoretical and technical knowledge about the design of complex nanostructures from MOF precursors.

Time, temperature and concentration resolved Yb3+ luminescence study in co-sputtered Cu2-xGaxS2 (0.1 < x < 1.6) thin films with a Cu–Ga composition gradient

The broad class of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials when doped with Yb3+ are interesting for thin film based luminescent solar concentrator (LSC's) application. In this work the strong and broad absorption properties of co-sputtered CuGaS2 (CGS) thin films combined with the luminescent properties of Yb are reported. Energy-dispersive x-ray spectroscopy (EDS), x-ray diffraction, transmission, excitation, and temperature dependent emission as well as radiative lifetime measurements are performed on thin films with varying Cu:Ga ratios and Yb3+ concentrations. It is found that Yb3+ emission can be broadly sensitized by the host in the range of 200–600 nm. A lower Cu:Ga ratio, crystallinity and post annealing in air provides a positive impact on the sensitization of Yb3+ emission. The temperature dependent time integrated decay curves show a clear thermal energy barrier of about 0.2 eV. Because the exponential tail, with a lifetime of 110 μs, is constant with temperature, we conclude that the barrier is connected to the thermal release of electrons trapped at the Yb2+ ground state. The low energy transfer efficiency from the host to the Yb dopant is attributed to efficient non-radiative electron-hole pair recombination. The prospects and design criteria of Cu(Al,Ga,In) (S,Se,Te)2 solar absorber materials for LSC applications is the further subject of the discussion.

UV-enhanced O2 sensing using β-Ga2O3 nanowires at room temperature

Oxygen sensors based on β-Ga2O3 nanowires were prepared by a chemical vapor deposition method and investigated in detail. β-Ga2O3 nanowires grew on sapphire substrate at 1100 °C with Au as a catalyst. The polycrystalline structure was confirmed according to the X-ray diffraction (XRD) patterns. Scanning electron microscope (SEM) images revealed the average diameter of the nanowires was 150 nm. The ratio of Ga to O was 0.765 according to energy dispersive spectroscopy (EDS) results. Photoluminescence emissions at 445 and 484 nm originated from oxygen vacancies and gallium-oxygen vacancy pairs. Both EDS results and photoluminescence revealed intrinsic oxygen vacancies in β-Ga2O3 nanowires. We coated the β-Ga2O3 nanowires on an interdigitated electrode to fabricated an oxygen sensor. Under ultraviolet light irradiation, at room temperature, the sensor’s response rise time and recovery time were 1034 s and 1283 s to 600 ppm oxygen, those were 1290 s and 1709 s to 1200 ppm oxygen. The mechanism of oxygen sensing was discussed.

Probing electronic and dielectric properties of ultrathin Ga2O3/Al2O3 atomic layer stacks made with in vacuo atomic layer deposition

Ultrathin (1–4 nm) films of wide-bandgap semiconductors are important to many applications in microelectronics, and the film properties can be sensitively affected by defects especially at the substrate/film interface. Motivated by this, an in vacuo atomic layer deposition (ALD) was developed for the synthesis of ultrathin films of Ga2O3/Al2O3 atomic layer stacks (ALSs) on Al electrodes. It is found that the Ga2O3/Al2O3 ALS can form an interface with the Al electrode with negligible interfacial defects under the optimal ALD condition whether the starting atomic layer is Ga2O3 or Al2O3. Such an interface is the key to achieving an optimal and tunable electronic structure and dielectric properties in Ga2O3/Al2O3 ALS ultrathin films. In situ scanning tunneling spectroscopy confirms that the electronic structure of Ga2O3/Al2O3 ALS can have tunable bandgaps (Eg) between ∼2.0 eV for 100% Ga2O3 and ∼3.4 eV for 100% Al2O3. With variable ratios of Ga:Al, the measured Eg exhibits significant non-linearity, agreeing with the density functional theory simulation, and tunable carrier concentration. Furthermore, the dielectric constant ε of ultrathin Ga2O3/Al2O3 ALS capacitors is tunable through the variation in the ratio of the constituent Ga2O3 and Al2O3 atomic layer numbers from 9.83 for 100% Ga2O3 to 8.28 for 100% Al2O3. The high ɛ leads to excellent effective oxide thickness ∼1.7–2.1 nm for the ultrathin Ga2O3/Al2O3 ALS, which is comparable to that of high-K dielectric materials.

Technologia reaktywnego rozpylania magnetronowego do otrzymywania azotków III

In the present work is studied synthesis of galium nitride (GaN) and aluminum nitride (AlN) by DC Reactive Magnetron Sputtering technology. As a sputtering target was used high purity (99.9999%) Gallium and Aluminum materials and as a reagent gas was used high purity (99.9999%) Nitrogen. Magnetron sputtering system with strong magnets (1450 mT) allows to make plasma at a low preasure 3 × 10-2 Pa and deposition process was carried out at high vacuum conditions. Deposited layers of GaN and AlN on the sappire substrate was analysed by X-ray diffraction (XRD) and revealed the crystalline nature highly oriented with the (0002) for both nitrides. For chemical composition was measured X-ray Photoelectron Spectroscopy (XPS) and it was found out the ratios of Ga:N and Al:N to be 1.07 and 1.04 respectively. For surface analysis was made Scanning Electron Microscopy (SEM). Optic transmission spectra showed band gaps to be 3.43 eV and 6.13 eV for GaN and AlN respectively.

Effect of Fe(III) on soybean protein-gallic acid hydrogel: Structure, functional properties, and digestive properties

A soy protein isolate-gallic acid (SPI-GA) complex was synthesized, mediated using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide. Different amounts of Fe3+ were then added to the SPI-GA complex to produce hydrogels (SPA@Fe) containing metal-phenolic network without heating the protein. Spectral analysis revealed that these hydrogels contained multiple modes of cross-linking, such as Schiff bases, hydrogen bonds, and coordination bonds. Coordination bonds formed between GA and Fe3+ mainly had a coordination number of three, and they changed the structure of the protein. Furthermore, these coordination bonds also endowed SPA@Fe with a more compact crosslinked network, thus improving the hydrogel's textural characteristics, thermal stability, storage modulus, and glucose adsorption capacity. The SPA@Fe hydrogel exhibited the best performance when the molar ratio of GA to Fe3+ was 1, with the thermal stability, hardness, springiness, and glucose adsorption capacity being 3.9, 1.84, 1.22, and 1.93 times higher than those of the SPI-GA hydrogel, respectively. Moreover, in-vitro digestion tests showed that SPA@Fe could control the release of loaded curcumin, had good capacity for adsorbing bile salt, and showed delayed degradation. This hydrogel system may offer a safe and feasible way to deliver bioactive substances such as curcumin.

Characterization and hydrolysis mechanism of soluble Al-Mg-Ga-Sn alloys in hydraulic fracturing applications

To engineer a dissolvable Al-Mg-Ga-Sn aluminum alloy material suitable for multi-stage hydraulic fracturing and sealing tools, an array of alloys was fabricated using high-temperature casting with varying concentrations of Ga and Sn. The compositions were designed such that the ratio of Ga to Sn remained constant at 1. The objective was to examine the influence of Ga and Sn content on the mechanical properties of the alloys and their reactivity with water. Results indicated that with 1.0 wt% of both Ga and Sn, the alloy displayed a ultimate tensile strength (σb) of 182±1 MPa, elongation (δ) of 33.8±0.8 %, reduction of area (φ) of 11.6±0.9 %, yield strength (σSc) of 161±1 MPa, relative compressibility (δ) of 63.0±1.0 %, and relative expansion of the cross-section (φ) of 170.8±0.9 %. Additionally, when subjected to water at 90℃, the alloy achieved a maximum dissolution rate of 3.0±1 g·h-1·cm-2. Upon contact with an aqueous environment, an electrochemical reaction ensues where aluminum atoms in the matrix lose electrons, transforming into Al3+ ions within the solution. Concurrently, Sn2+ and Ga2+ ions migrate to the surface oxide film, substituting Al3+ ions at the grain boundaries, which induces vacancies in the oxide film, reducing its resistance to further ionic penetration and densification loss. This study elucidates the macroscopic process mechanism of the interaction between water-soluble alloys and aqueous media, and proposes a corresponding microscopic mechanism.

Analysis of the Influence of Peripheral Light Shelves on Building Lighting

Due to the design problems in modern architecture, it often appears that although the sunlight of the building is sufficient, the lighting quality of the building interior is not good. Due to the reasons of lighting, shading and interior layout, the phenomenon of glare and uneven distribution of light often occurs in buildings. Therefore, it is recommended to use light shelves to reduce problems such as glare and improve the indoor light environment comfort. The effects of six different widths and five different heights of peripheral light shelves on DF, UDI, GA and Uniformity Ratio of Daylighting are analyzed. The results show that the width and height of light shelves have no improvement effect on DF. The height of the light shelves has an improvement effect on indoor UDI, but the width does not; The width and height of light shelves can improve GA and Uniformity Ratio of Daylighting.

High-quality Cr2O3 - Ga2O3 solid solutions films grown by mist-CVD epitaxy

Micron-thick layers of (Cr1-xGax)2O3 solid solutions were grown by modified mist chemical vapor deposition (mist-CVD) with three different Ga concentrations. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods were used to analyze the quality of the films. They showed good crystallinity, homogeneity and coalescence of the samples. Solid solution contents estimation was performed via applying Vegard’s law to XRD data and by its results the highest reached Cr:Ga ratio is approximately 1:1. Transmission spectra of solid solutions demonstrated blue-shift of the absorption edge with increase of the Ga contents. Optical bandgap increased from 3.06 eV for undoped Cr2O3 sample to 3.73 eV for the layer with the highest Ga concentration.

Control of Surface Chemistry in Recess Etching toward Normally Off GaN Metal–Insulator–Semiconductor High‐Electron‐Mobility Transistors

Reducing off‐state and gate leakage current is crucial in the development of metal–insulator–semiconductor high‐electron‐mobility transistors (MIS‐HEMTs). This work reports interface engineering in the gate recess region through low‐damage digital etching during the fabrication of normally off GaN MIS‐HEMTs. Conventional plasma etching leads to a reduction of the N/(Al+Ga) ratio, but this value recovers to almost 1 with optimized oxidation condition during digital etching, suggesting a reduction of the Al/Ga dangling bonds based on the proposed technique. GaN MIS‐HEMTs with digital etching exhibits a threshold voltage of 1.0 V at 1 μA mm−1, a high ON/OFF current ratio of 1010, a gate breakdown voltage of 22 V, and a low gate leakage current of 10−8 mA mm−1.

IGZO thin films deposited by ultrasonic spray pyrolysis: effect of Zn precursor milling and In and Ga concentration

Codoped zinc oxide thin films with indium and gallium (IGZO) were deposited on soda-lime glass substrates by the ultrasonic chemical spray (USP) technique. The influence of the mechanical grinding process of Zn precursor (zinc acetate, AcZn) and the In and Ga concentrations was analyzed. The grinding process was carried out in a planetary ball mill, with a ball:/precursor ratio of 4:1, and a constant rotation speed of 300 RPM. The starting solutions were prepared at a molar concentration of 0.2 and variable In and Ga atomic concentration (1, 1.5, 2, 2.5 and 3 at%). The deposition conditions were kept constant, substrate temperature of 450 °C and deposition time of 7 min. Structural, morphological, optical, and electrical properties were analyzed. From the structural analysis a preferential orientation along the (101) plane for dominant In concentrated IGZO films was observed, whereas for dominant Ga concentrated was the (002) plane. The average optical transmission was in the range of 83–90%, confirming the high transparency of all the deposited films. The bandgap values, Eg, showed slight variations, from 3.43 to 3.53 eV. The best electrical properties were obtained in the IGZO films with an In:Ga ratio of 1.5:1 [IGZO(1.5:1)], evaluated by the figure of merit, 3.50 × 10–3 (Ω/□)−1, calculated for an optical transmission of 86% and a sheet resistance of 63 Ω/□. According to the obtained results, the IGZO thin films deposited by the USP technique, are potentially applicable in the field of optoelectronics, mainly as transparent electrode.

Transformation of Light Alkanes into High-Value Aromatics

This research work is focused on the transformation of light alkane (propane) into high-value aromatics using gallo-alumino-silicate catalysts. Two sets of gallo-alumino-silicates were synthesized for this study. In the first set, the ratio of Ga/(Al+Ga) was modified, while the Si/(Al+Ga) ratio was held constant. In the subsequent set, the Si/(Al+Ga) ratio was adjusted, while maintaining a consistent Ga/(Al+Ga) ratio. This approach aimed to directly assess the impact of each ratio on catalyst performance. The comprehensive characterization of all catalysts was conducted using various instrumental techniques, i.e., BET surface area, XRD, NH3-TPD, 27Al, 71Ga and 29Si MAS NMR, and XPS. A gradual reduction in the percentage of crystallinity and rise in meso-surface area was noticed with a rise in Ga/(Al+Ga) ratio. The total acidity (NH3-TPD) demonstrated a decline as the Si/(Al+Ga) ratio increased, attributed to an overall decline in Al3+ or Ga3+ species. The XPS intensity of the Ga 2p3/2 peak rose in correlation with an elevated ratio of Ga/(Al+Ga), suggesting the formation of extra-framework Ga species. The propane conversion, aromatic yield, and aromatization/cracking ratio exhibited an increase with an increasing Ga/(Al+Ga) ratio, reaching an optimum value of 0.46 before declining. Conversely, an appreciable drop in the conversion of propane and yield of aromatics was detected with the rise in Si/(Al+Ga) ratio, attributing to the decline in acidity. The catalyst having a Ga/(Al+Ga) ration of 0.46 exhibited the highest propane conversion and aromatic yield of 83.0% and 55.0% respectively.

L-shaped association between the GA/HbA1c ratio and all-cause mortality in U.S. adults with NAFLD: a cross-sectional study from the NHANES 1999–2004

ObjectiveIt is currently unclear whether there is a relationship between the ratio of glycated albumin to hemoglobin A1c (GA/HbA1c) and mortality in individuals diagnosed with nonalcoholic fatty liver disease (NAFLD). The primary objective of the study was to investigate the relationship between the GA/HbA1c ratio and all-cause mortality in adults with NAFLD in the U.S.MethodsThe investigation included a total of 5,295 individuals aged ≥ 18 years who were diagnosed with NAFLD, these individuals were selected from the National Health and Nutrition Examination Survey conducted between 1999 and 2004. To evaluate the outcomes of death, the researchers relied on National Death Index (NDI) records up to December 31, 2019. To better understand the nonlinear relationship between the GA/HbA1c ratio and mortality among individuals with NAFLD, this study employed both subgroup and sensitivity analyses. Furthermore, Cox proportional hazards models and two-part Cox proportional hazards model were utilized.ResultsThe study included a total of 5,295 adult patients with NAFLD in the U.S. During a median follow-up period of 16.9 years, there were 1,471 recorded deaths, including 419 cardiovascular deaths. After accounting for various factors, a higher GA/HbA1c ratio exhibited a positive and nonlinear association with an increased risk of all-cause mortality in patients with NAFLD. Furthermore, the study revealed an L-shaped relationship between the GA/HbA1c ratio and all-cause mortality, with the inflection point occurring at a GA/HbA1c ratio of 2.21. When the GA/HbA1c ratio exceeded 2.21, each 1-unit increase in the ratio was associated with a 33% increase in the adjusted hazard ratio (HR 1.33; 95% CI 1.14, 1.60) for all-cause mortality.ConclusionsA nonlinear correlation between the ratio of GA to HbA1c and all-cause mortality was observed in U.S. adults with NAFLD. In addition, an elevated GA/HbA1c ratio was linked to an increased risk of all-cause mortality in these patients.

Burst Release from In Situ Forming PLGA-Based Implants: 12 Effectors and Ways of Correction.

This systematic review examines the reasons for the phenomenon of active ingredient "burst" release, which is a major drawback of PLGA-based in situ formed implants, and the likely ways to correct this phenomenon to improve the quality of in situ formed implants with a poly(DL-lactide-co-glycolide) matrix. Actual and relevant publications in PubMed and Google Scholar databases were studied. The concept of the review was based on the theory developed during literature analysis of 12 effectors on burst release from in situ forming implants based on PLGA. Only those studies that sufficiently fully disclosed one or another component of the theory were included. The analysis resulted in development of a systematic approach called the "12 Factor System", which considers various constant and variable, endogenous and exogenous factors that can influence the nature of 'burst release' of active ingredients from PLGA polymer-based in situ formed implants. These factors include matrix porosity, polymer swelling, LA:GA ratio, PLGA end groups, polymer molecular weight, active ingredient structure, polymer concentration, polymer loading with active ingredients, polymer combination, use of co-solvents, addition of excipients, and change of dissolution conditions. This review also considered different types of kinetics of active ingredient release from in situ formed implants and the possibility of using the "burst release" phenomenon to modify the active ingredient release profile at the site of application of this dosage form.

Effect of Channel Shape on Performance of Printed Indium Gallium Zinc Oxide Thin-Film Transistors.

Printing technology will improve the complexity and material waste of traditional deposition and lithography processes in device fabrication. In particular, the printing process can effectively control the functional layer stacking and channel shape in thin-film transistor (TFT) devices. We prepared the patterning indium gallium zinc oxide (IGZO) semiconductor layer with Ga, In, and Zn molar ratios of 1:2:7 on Si/SiO2 substrates. And the patterning source and drain electrodes were printed on the surface of semiconductor layers to construct a TFT device with the top contact and bottom gate structures. To overcome the problem of uniform distribution of applied voltages between electrode centers and edges, we investigated whether the circular arc channel could improve the carrier regulation ability under the field effect in printed TFTs compared with a traditional structure of rectangular symmetry and a rectangular groove channel. The drain current value of the IGZO TFT with a circular arc channel pattern was significantly enhanced compared to that of a TFT with rectangular symmetric source/drain electrodes under the corresponding drain-source voltage and gate voltage. The field effect properties of the device were obviously improved by introducing the arc-shaped channel structure.

MWCNTs dispersion adopting GA and its application towards copper tailings-based cementitious materials

Hydrophobic carbon nanotubes are hardly to disperse in water and prone to agglomerate when poured with Copper Tailing-Based Cementitious Material (CTCM). Multi-walled carbon nanotubes (MWCNTs) + Arabic Gum (GA) dispersions were prepared by a novel method of synergistic optimization of concentration, controlling low-frequency ultrasonic time and setting the ambient temperature with non-toxic anionic surfactant GA as surfactant. The results of UV–Vis spectroscopy showed that the high stability MWCNTs + GA dispersion with low aggregation area (< 1.2%) and low aggregation beam size (< 219 nm) have been prepared by using 1.7 mmol/l GA. The effects of highly stable MWCNTs dispersion on the mechanical properties, microstructure and durability of CTCM were studied. The 28 days compressive strength increased by 21.5%, and the flexural strength increased by 20.5%, almost reaching the mechanical level of the control group. The results of SEM, XRD and EDS showed that GA significantly enhanced the dispersion of MWCNT in aqueous solution at a suitable concentration (mass ratio of GA:CNTs = 1:1). The microstructure of the prepared CTCM by high stability MWCNTs dispersion was optimized obviously, and the mechanical properties and durability were improved significantly. This method solves the dual problem of MWCNTs not being fully dispersed in aqueous solution and being easily re-agglomerated in cementitious materials, as well as finding a breakthrough for the low cost and industrialization of tailings cement-based composite cementitious materials.

Influence of Channel Surface with Ozone Annealing and UV Treatment on the Electrical Characteristics of Top-Gate InGaZnO Thin-Film Transistors.

The effect of the channel interface of top-gate InGaZnO (IGZO) thin film transistors (TFTs) on the electrical properties caused by exposure to various wet chemicals such as deionized water, photoresist (PR), and strippers during the photolithography process was studied. Contrary to the good electrical characteristics of TFTs including a protective layer (PL) to avoid interface damage by wet chemical processes, TFTs without PL showed a conductive behavior with a negative threshold voltage shift, in which the ratio of Ga and Zn on the IGZO top surface reduced due to exposure to a stripper. In addition, the wet process in photolithography increased oxygen vacancy and oxygen impurity on the IGZO surface. The photo-patterning process increased donor-like defects in IGZO due to organic contamination on the IGZO surface by PR, making the TFT characteristics more conductive. The introduction of ozone (O3) annealing after photo-patterning and stripping of IGZO reduced the increased defect states on the surface of IGZO due to the wet process and effectively eliminated organic contamination by PR. In particular, by controlling surface oxygens on top of the IGZO surface excessively generated with O3 annealing using UV irradiation of 185 and 254 nm, IGZO TFTs with excellent current-voltage characteristics and reliability could be realized comparable to IGZO TFTs containing PL.

Photoluminescence Property of Cu(In,Ga)S2 Quantum Dots Depending on Their Composition and Nanostructure

Multinary quantum dots (QDs) composed of less toxic elements, such as CuInS2 and AgInS2, have been intensively investigated for the application to highly efficient solar energy conversion systems and novel luminescent devices, because their electronic energy structure and optical properties can be controlled by the size and chemical composition of QDs. Recently we have successfully prepared alloy QDs composed of Ag–In–Ga–S and Ag–In–Ga–Se semiconductors, the Eg of which was tunable in the visible and near-IR wavelength regions, respectively [1, 2]. These QDs exhibited a narrow PL peak assignable to the band-edge emission and their peak wavelengths were widely tunable by changing their Eg. However, there have been few investigations to prepare Cu-based multinary QDs with a narrow PL peak. Thus, in this study, we prepare spherical QDs composed of less-toxic Cu–In–Ga–S (CIGS) alloy semiconductor and investigate their composition-dependent optical properties.The synthesis of CIGS QDs was carried out by our previous heating-up method with a slight modification [1]. Powders of Cu(OAc)2, In(acac)3, Ga(acac)3, elemental sulfur were dispersed in a mixture solution of oleylamine and dodecanethiol, followed by the heat treatment at 300 oC. The resulting solution was subjected to centrifugation to remove large precipitates, and QDs were isolated from the supernatant by adding methanol as a non-solvent. Thus-obtained QDs were used as a core to prepare cores-shell-structured particles, in which the surface of CIGS core was coated by thin shell composed of ZnS or GaSx.The chemical composition of obtained QDs was controlled by the fractions of individual metal salts used as precursors. The Cu/(In+Ga) and In/(In+Ga) of obtained QDs roughly agreed with those used in preparation. The obtained QDs were spherical and their average diameter decreased from 5.4 nm to 3.4 nm with an increase in the In fraction. The absorption spectra of CIGS QDs were varied depending on both the fractions of Cu and In. The onset wavelength of QDs was blue-shifted from 840 nm to 540 nm with a decrease in the Cu/(In+Ga) in preparation from 0.7 to 0.1 when the QDs were prepared with the fixed ratio of In/(In+Ga)= 0.7. On the other hand, the QDs exhibited a blue shift of absorption onset from ca. 750 nm to 480 nm with a decrease in In/(In+Ga) ratio from 1.0 to 0 under the fixed Cu fraction in preparation, Cu/(In+Ga)= 0.3. The obtained Eg monotonously decreased from 2.77 eV to 1.74 eV with an increase in In/(In+Ga) ratio from 0 to 1.0, and these values were larger than those of corresponding bulk semiconductors due to the quantum size effect. From the ionization energy of the QDs evaluated from the onset energy of the photoelectron yield spectra in air, we determined the electronic energy structure of CIGS QDs. With a decrease in the Eg of QDs, the conduction band minimum level shifted to a lower level from ca. –2.3 eV to –3.4 eV, while the valence band maximum level was almost constant to ca. 5.1–5.2 eV.Surface coating of CIGS QDs with other semiconductor shells increased the photoluminescence (PL) intensity. The ZnS shell coating to form CIGS@ZnS core-shell QDs produced a PL peak at 649 nm (FWHM: 0.47 eV), being much broader than that of CIGS cores (FWHM: 0.23 eV) because of alloying at the interface between ZnS shell and CIGS core, though the PL quantum yield (QY) increased to 30% from 8%. In contrast, the GaSx coating on CIGS QD surface enlarged the intensity of PL peak without changing its peak width: CIGS@GaSx QDs exhibited a narrow PL peak (FWHM: 0.20 eV) at 671 nm, being comparable to the PL peak of CIGS QDs (the peak wavelength of 675 nm and the FWHM of 0.23 eV). The PL QY was also increased to 27% from 8% by the GaSx coating on CIGS QDs. The tunabilities of electronic energy structure and PL property of CIGS QDs are useful for constructing efficient light energy conversion systems and luminescent devices.[1] T. Kameyama, et al., ACS Applied. Mater. Interfaces 2018, 10, 42844-42855.[2] T. Kameyama, et al., ACS Appl. Nano Mater. 2020, 3, 3275-3287.

Control of electronic structure in (Cu, Ag)(Ga, In)Se2 for high efficiency solar cells

A three-dimensional (3D) band-gap energy (E g) map was constructed for a (Cu1−y Ag y )(Ga x In1−x )Se2 (CAGISe) system. This system’s E g increases monotonically from CuInSe2 (CISe) as the ratios of both Ga/(Ga+In) [GGI], x, and Ag/(Cu+Ag) [ACA], y, increase. Furthermore, the energy levels of the VB maximum (VBM) and the conduction band minimum (CBM) were also mapped in 3D. In this CAGISe system, there is no significant change in VBM, whereas CBM does show an increase as the GGI ratio increases. However, as the ACA ratio increases, there is a decrease in VBM level but no significant change in CBM. The substitution effects of Ga for In and Ag for Cu in CISe are discussed on the basis of “principles of orbital interaction.”