Gallium Acetylacetonate Research Articles

Thick β-Ga2O3 homoepitaxial films grown on ([formula omitted]01) substrate by mist-CVD

Thick β-Ga2O3 homoepitaxial films have been grown on (2¯01) commercial substrates by mist-CVD with gallium acetylacetonate precursor for the first time. The growth rate of about 2 μm/h has been reached, which is unavailable for any other known epitaxial technique. The layer is characterized by the constant thickness and reasonable structure quality due to low stressed interface.

An Aerosol-Assisted Chemical Vapor Deposition Route to Tin-Doped Gallium Oxide Thin Films with Optoelectronic Properties.

Gallium oxide is a wide-bandgap compound semiconductor material renowned for its diverse applications spanning gas sensors, liquid crystal displays, transparent electrodes, and ultraviolet detectors. This paper details the aerosol assisted chemical vapor deposition synthesis of tin doped gallium oxide thin films using gallium acetylacetonate and monobutyltin trichloride dissolved in methanol. It was observed that Sn doping resulted in a reduction in the transmittance of Ga2O3 films within the visible spectrum, while preserving the wide bandgap characteristics of 4.8 eV. Furthermore, Hall effect testing revealed a substantial decrease in the resistivity of Sn-doped Ga2O3 films, reducing it from 4.2 × 106 Ω cm to 2 × 105 Ω cm for the 2.5 at. % Sn:Ga2O3 compared to the nominally undoped Ga2O3.

Growth of α-Ga2O3 from Gallium Acetylacetonate under HCl Support by Mist Chemical Vapor Deposition.

α-Ga2O3 films were grown on a c-plane sapphire substrate by HCl-supported mist chemical vapor deposition with multiple solution chambers, and the effect of HCl support on α-Ga2O3 film quality was investigated. The growth rate monotonically increased with increasing Ga supply rate. However, as the Ga supply rate was higher than 0.1 mmol/min, the growth rate further increased with increasing HCl supply rate. The surface roughness was improved by HCl support when the Ga supply rate was smaller than 0.07 mmol/min. The crystallinity of the α-Ga2O3 films exhibited an improvement with an increase in the film thickness, regardless of the solution preparation conditions, Ga supply rate, and HCl supply rate. These results indicate that there is a low correlation between the improvement of surface roughness and crystallinity in the α-Ga2O3 films grown under the conditions described in this paper.

Oxygen vacancies modulating performance for Ga2O3 solar-blind photodetectors via low-cost mist chemical vapor deposition

The wide bandgap and excellent chemical and physical properties of gallium oxide (Ga2O3) make it an ideal and natural material for solar-blind photodetectors (SBPDs). However, the development of Ga2O3-based SBPDs in practical applications was hindered by intrinsic oxygen vacancies (VO) in Ga2O3 films, high process requirements, and expensive equipment. Here, VO concentration in the films can be regulated by the introducing of O2 in the carrier gases using the mist chemical vapor deposition (Mist-CVD), which has the benefits of low cost, vacuum-free, and easy procedure. The high-performance Ga2O3 films exhibit a single-crystal tendency and low VO concentration under the Ar (1 L/min) and O2 (0.5 L/min) flow rates at 600 °C. The photodetectors exhibit a large photo-to-dark current ratio of 3.0 × 107, a high specific detectivity of 3.06 ×1011 Jones, and a fast response speed of 0.528/0.158 s at 500 μWcm−2 light intensities at 5 V. The mechanism of VO regulation in Ga2O3 films was demonstrated by adjusting the carrier gas flow rates. We also clarified the effect of VO on the dark current and photocurrents of the devices. The low-cost and straightforward Mist-CVD can provide an effective method to grow high-quality Ga2O3 films, further facilitating their practical application.

Fabrication of 3D-printed scaffolds loaded with gallium acetylacetonate for potential application in osteoclastic bone resorption

We recently reported the potential of a new gallium compound, gallium acetylacetonate (GaAcAc) in combating osteoclastic bone resorption through inhibition of osteoclast differentiation and function. Herein, we focused on 3D-printed polylactic acid scaffolds that were loaded with GaAcAc and investigated the impact of scaffold pretreatment with polydopamine (PDA) or sodium hydroxide (NaOH). We observed a remarkable increase in scaffold hydrophilicity with PDA or NaOH pretreatment while biocompatibility and in vitro degradation were not affected. NaOH-pretreated scaffolds showed the highest amount of GaAcAc loading when compared to other scaffolds (p < 0.05). NaOH-pretreated scaffolds with GaAcAc loading showed effective reduction of osteoclast counts and size. The trend was supported by suppression of key osteoclast differentiation markers such as NFAT2, c-Fos, TRAF6, & TRAP. All GaAcAc-loaded scaffolds, regardless of surface pretreatment, were effective in inhibiting osteoclast function as evidenced by reduction in the number of resorptive pits in bovine cortical bone slices (p < 0.01). The suppression of osteoclast function according to the type of scaffold followed the ranking: GaAcAc loading without surface pretreatment > GaAcAc loading with NaOH pretreatment > GaAcAc loading with PDA pretreatment. Additional studies will be needed to fully elucidate the impact of surface pretreatment on the efficacy and safety of GaAcAc-loaded 3D-printed scaffolds.

Heteroepitaxial growth of Ga2O3 on 4H-SiC by liquid-injection MOCVD for improved thermal management of Ga2O3 power devices

We report on the growth of monoclinic β- and orthorhombic κ-phase Ga2O3 thin films using liquid-injection metal-organic chemical vapor deposition on highly thermally conductive 4H-SiC substrates using gallium (III) acetylacetonate or tris(2,2,6,6-tetramethyl-3,5-heptanedionato) gallium (III). Both gallium precursors produced the β phase, while only the use of the latter led to growth of κ-Ga2O3. Regardless of the used precursor, best results for β-Ga2O3 were achieved at a growth temperature of 700 °C and O2 flows in the range of 600–800 SCCM. A relatively narrow growth window was found for κ-Ga2O3, and best results were achieved for growth temperatures of 600 °C and the O2 flow of 800 SCCM. While phase-pure β-Ga2O3 was prepared, κ-Ga2O3 showed various degrees of parasitic β phase inclusions. X-ray diffraction and transmission electron microscopy confirmed a highly textured structure of β- and κ-Ga2O3 layers resulting from the presence of multiple in-plane domain orientations. Thermal conductivities of 53 nm-thick β-Ga2O3 (2.13 + 0.29/−0.51 W/m K) and 45 nm-thick κ-Ga2O3 (1.23 + 0.22/−0.26 W/m K) were determined by transient thermoreflectance and implications for device applications were assessed. Presented results suggest great potential of heterointegration of Ga2O3 and SiC for improved thermal management and reliability of future Ga2O3-based high power devices.

Rapid epitaxy of 2-inch and high-quality α-Ga2O3 films by mist-CVD method

High thickness uniformity and large-scale films of α-Ga2O3 are crucial factors for the development of power devices. In this work, a high-quality 2-inch α-Ga2O3 epitaxial film on c-plane sapphire substrates was prepared by the mist-CVD method. The growth rate and phase control mechanisms were systematically investigated. The growth rate of the α-Ga2O3 films was limited by the evaporation of the microdroplets containing gallium acetylacetonate. By adjusting the substrate position (z) from 80 to 50 mm, the growth rate was increased from 307 nm/h to 1.45 μm/h when the growth temperature was fixed at 520 °C. When the growth temperature exceeded 560 °C, ε-Ga2O3 was observed to form at the edges of 2-inch sapphire substrate. Phase control was achieved by adjusting the growth temperature. When the growth temperature was 540 °C and the substrate position was 50 mm, the full-width at half maximum (FWHM) of the rocking curves for the (0006) and (10-14) planes were 0.023° and 1.17°. The screw and edge dislocations were 2.3 × 106 and 3.9 × 1010 cm-2, respectively. Furthermore, the bandgaps and optical transmittance of α-Ga2O3 films grown under different conditions were characterized utilizing UV-visible and near-IR scanning spectra.

Efficacy assessment of methylcellulose-based thermoresponsive hydrogels loaded with gallium acetylacetonate in osteoclastic bone resorption.

Homeostatic imbalance involving progressive stimulation of osteoclast (OC) differentiation and function will lead to an increased risk of fragility fractures. In this regard, we investigated gallium acetylacetonate (GaAcAc) as a possible treatment for osteoclastic bone resorption. Further, the extent to which suitable delivery systems can enhance the therapeutic potential of GaAcAc was evaluated. GaAcAc solution (10-50µg/mL) suppressed OC differentiation using murine monocytic RAW 264.7 or hematopoietic stem cells. Methylcellulose-based hydrogels were fabricated and characterized based on biocompatibility with bone cells, GaAcAc loading, and thermoresponsive behavior using storage (G') and loss (G″) moduli parameters. Compared to GaAcAc solution, hydrogels loaded with GaAcAc (GaMH) were more effective in suppressing OC differentiation and function. The number and extent of bone resorption pits from ex vivo studies were markedly reduced with GaMH treatment. Mechanistic assessment of GaMH efficacy showed superiority, compared to GaAcAc solution, in downregulating the expression of key markers involved in mediating OC differentiation (such as NFAT2, cFos, TRAF6, and TRAP) as well as in bone resorption by OCs (cathepsin K or CTSK). Additional studies (in vitro and in vivo) suggested that the performance of GaMH could be ascribed to controlled release of GaAcAc and the ability to achieve prolonged bio-retention after injection in BALB/c mice, which plausibly maximized the therapeutic impact of GaAcAc. Overall, the work demonstrated, for the first time, the therapeutic efficacy of GaAcAc and the therapeutic potential of GaMH delivery systems in osteoclastic bone resorption.

Method development for determination of organic fluorine in gasoline and its components using high-resolution continuum source flame molecular absorption spectrometry with gallium fluoride as a target molecule

High-resolution continuum source molecular absorption spectrometry (HR-CS MAS) has been developing fast for fluorine determination, but neither flame nor graphite furnace technique have ever been applied for the analysis of petroleum or its products. Hydrogen fluoride can be applied in technologies of gasoline components production, unfortunately, arising organic fluorides can contaminate final product. The aim of this work was development of fast and simple HR-CS MAS method, with an ordinary air-acetylene flame, for determination of organic F in gasoline and its components. Gallium fluoride as a target molecule was the imposing choice, because Ga undergoes atomization at relatively low temperature, and the GaF molecule is known to provide good sensitivity in F determination. Severe difficulties have arisen to get higher concentration of gallium (as Ga(III)acetylacetonate) in the measured (xylene) solution. Furthermore, depending on the flame character, the spectrum of the GaF molecule at the most sensitive 211.248 nm rotational “line”could have been disturbed by intensive noise (a case of too rich flame) or overlapped by the OH molecule spectrum (a case of too lean flame). The effects, as well as sensitivity of F determination, depended on the sample volatility and its dilution ratio. The difficulties have been overcome by adjusting the solution aspiration rate and the additional air flow rate to get not-disturbed baseline. The least square background correction (LSBC) with the OH molecule spectrum as the correction spectrum (the OH molecule spectrum intentionally generated for the first time) and the standard addition calibration have been also applied. Huge difference in sensitivity, up to one order of magnitude, depending on the F compound volatility and its chemical character was stated. A standard giving the best sensitivity (heptafluorobutanol) turned out to be the most suitable for calibration in analysis of real samples (satisfactory agreement with results of combustion ion chromatography). It was found that HF introduced into the solution of the investigated sample does not contribute to the increase of F signal. Using 5000 mg L−1 of Ga in a solution, the best characteristic concentration and detection limit are 3.2 mg L−1 and 0.93 mg L−1, respectively. The developed method enabled to identify high contamination of some gasoline components with organic F species, which constituted significant corrosion and environmental threat.

Method for organic fluorine determination in gasoline and its components using high-resolution continuum source flame molecular absorption spectrometry with gallium fluoride as a target molecule

Organic fluorides can arise due to the usage of HF in technologies of gasoline production, therefore, it is necessary to identify contamination of gasoline or its components with organic fluorine. For this aim, simple and fast method is proposed. The method relies on sample dilution in xylene, followed by the solution aspiration to a high-resolution continuous source spectrometer for measurement of absorption of radiation by GaF molecule, arisen in air-acetylene flame. Gallium(III) acetylacetonate is carefully dissolved and introduced to all measured solutions at Ga concentration 5000 mg L−1. For standard addition calibration three types of samples solutions are prepared to contain: none, 50 mg L−1 and 100 mg L−1 of added fluorine. As fluorine standard 2, 2, 3, 3, 4, 4, 4-heptafluoro-1-pentanol is applied. The lowest possible flow rate of acetylene is recommended. The solution flow rate and the additional air flow rate should be adjusted to obtain not-disturbed baseline. The overlap of the GaF signal with residual signal of the OH molecule can be overcome using least square background correction. Five pixels are recommended for signal evaluation at the most sensitive 211.248 nm rotational “line”. Using such conditions characteristic concentration was 3.2 mg L−1. Detection limit recalculated for initial sample was 4-10 mg L−1.•High-resolution continuum source flame molecular absorption spectrometry turned out to be an excellent tool for determination of pollution of gasoline with organic fluorine.•Due to application of GaF as a target molecule, it is possible to use a low-temperature and easy for operation air-acetylene flame.•The proposed method can be applied for analysis of alkylate, reformate, isomerizate, ethanol as well as commercial automotive and aviation gasoline.

Annealing induced surface restructuring in hydrothermally synthesized gallium oxide nano-cuboids

Gallium Oxide (Ga2O3) nanostructures are synthesized using a hydrothermal approach and the effect of different gallium precursors on the morphology of gallium nanostructures is studied. The rice-like nanostructures are obtained in gallium chloride and gallium nitrate precursors, whereas nano-cuboids are formed in the case of gallium acetylacetonate. The size of the edge defined nano-cuboid is in the range of 0.6 μm × 0.3 μm × 0.2 μm. The as-synthesized nano-cuboids are in the metastable phase “α” and converts to a stable “β” phase after annealed at a higher temperature (~850 °C). Post synthesis thermal annealing also results in the creation of nanopores on the surface of these nano-cuboids. Pores size increases with an increase in annealing temperature till 950 °C, further increase in annealing temperature reduces the size of pores and a smoother surface appeared. The annealing induced surface restructuring offers significant alteration on nano-cuboid properties that could be beneficial for surface-related applications.

Growth of α- and β-Ga2O3 epitaxial layers on sapphire substrates using liquid-injection MOCVD

Ga2O3, a wide-bandgap semiconductor material, offers a great potential for power and high-voltage electronic devices. We report on the growth of undoped α- and β-phase Ga2O3 using liquid-injection metal-organic chemical vapor deposition (LI-MOCVD) on sapphire substrates. Using the same precursor (gallium acetylacetonate) and deposition temperature of 700 °C, the phase selection was controlled by the sapphire substrate orientation, where the growth of α- and β-phase Ga2O3 was achieved on m- and c-plane surface, respectively. As deduced from x-ray diffraction, α-Ga2O3 films show epitaxial character, while β- Ga2O3 films exhibit highly textured structure. Oxygen flow was also found to have a strong impact on the phase purity of α-Ga2O3 for the flow rates examined. Optical and electrical properties of the layers grown at different oxygen flow rates were also studied systematically. LI-MOCVD growth of α-phase Ga2O3 layers at relatively high deposition temperature widens the high-temperature processing of the Ga2O3-based electronic and optoelectronic devices.

Light-Activated Chemoresistive and Plasmonic-Resonant Optical Sensors for NO2 and H2 Sensing Based on ZnO Doped Nanoparticles

Light-Activated Chemoresistive and Plasmonic-Resonant Optical Sensors for NO2 and H2 Sensing Based on ZnO Doped Nanoparticles

Optical Properties of Mist CVD Grown α-Ga2O3

We report on the study of optical properties of mist CVD grown alpha Gallium oxide with the observation of excitonic absorption in spectral responsivity measurements. 163 nm of Gallium oxide was grown on sapphire using Gallium acetylacetonate as the starting solution at a substrate temperature of 450 deg C. The film was found to be crystalline and of alpha phase with an on axis full width at half maximum of 92 arcsec as confirmed from X ray diffraction scans. The Taucs plot extracted from absorption spectroscopy exhibited two transitions in the UV regime at 5.3 eV and 5.6 eV, corresponding to excitonic absorption and direct band to band transition respectively. The binding energy of exciton was extracted to be 114 meV from spectral responsivity measurements. Further, metal semiconductor metal photodetectors with lateral inter digitated geometry were fabricated on the film. A sharp band edge was observed at 230 nm in the spectral response with peak responsivity of around 1 Amperes per Watt at a bias of 20 V. The UV to visible rejection ratio was found to be around 100 while the dark current was measured to be around 0.1 nA.

Synthesis and Polymorphism of Mixed Aluminum-Gallium Oxides.

The synthesis of a new solid solution of the oxyhydroxide Ga5–xAlxO7(OH) is investigated via solvothermal reaction between gallium acetylacetonate and aluminum isopropoxide in 1,4-butanediol at 240 °C. A limited compositional range of 0 ≤ x ≤ 1.5 is produced, with the hexagonal unit cell parameters refined from powder X-ray diffraction (XRD) showing a linear contraction in unit cell volume with an increase in Al content. Solid-state 27Al and 71Ga nuclear magnetic resonance (NMR) spectroscopies show a strong preference for Ga to occupy the tetrahedral sites and Al to occupy the octahedral sites. Using isopropanol as the solvent, γ-Ga2–xAlxO3 defect spinel solid solutions with x ≤ 1.8 can be prepared at 240 °C in 24 h. These materials are nanocrystalline, as evidenced by their broad diffraction profiles; however, the refined cubic lattice parameter shows a linear relationship with the Ga:Al content, and solid-state NMR spectroscopy again shows a preference for Al to occupy the octahedral sites. Thermal decomposition of Ga5–xAlxO7(OH) occurs via poorly ordered materials that resemble ε-Ga2–xAlxO3 and κ-Ga2–xAlxO3, but γ-Ga2–xAlxO3 transforms above 750 °C to monoclinic β-Ga2–xAlxO3 for 0 ≤ x ≤ 1.3 and to hexagonal α-Ga2–xAlxO3 for x = 1.8, with intermediate compositions of 1.3 < x < 1.8 giving mixtures of the α- and β-polymorphs. Solid-state NMR spectroscopy shows only the expected octahedral Al for α-Ga2–xAlxO3, and for β-Ga2–xAlxO3, the ∼1:2 tetrahedral:octahedral Al ratio is in good agreement with the results of Rietveld analysis of the average structures against powder XRD data. Relative energies calculated by periodic density functional theory confirm that there is an ∼5.2 kJ mol–1 penalty for tetrahedral rather than octahedral Al in Ga5–xAlxO7(OH), whereas this penalty is much smaller (∼2.0 kJ mol–1) for β-Ga2–xAlxO3, in good qualitative agreement with the experimental NMR spectra.

Gallium - a versatile element for tuning the photoluminescence properties of InP quantum dots.

With the goal to tune the emission properties of colloidal InP quantum dots, the incorporation of Ga was explored. Unexpectedly, depending on the nature of the gallium precursor, the photoluminescence shifted either to the red (gallium oleate) or to the blue (gallium acetylacetonate). In the first case, larger-sized InP/GaP core/shell nanocrystals were formed, while in the second case the formation of an InGaP alloy structure enabled the blue range of emission (475 nm) to be accessed.

Controlling the white phosphorescence ZnGa2O4 phosphors by surface defects

White phosphorescence that lasted ≈ 212 s, being the longest phosphorescence time reported so far for any Ga based material, has been observed in undoped ZnGa2O4 (ZGO) phosphors. The samples were synthesized by a simple combustion method by using two different Gallium precursors (Gallium nitrate and Gallium Acetylacetonate). According to the X-ray diffraction analysis, the samples prepared with the two different precursors presented the same single cubic phase. TEM images demonstrated that the ZGO phosphors made with both precursors are formed by nanoparticles with quasi-spherical shape, and they have nanoparticle sizes in the range of 17–43 nm. When excited with UV light (400 nm), these phosphors produced a broad blue-green-yellow luminescence. The blue band was associated to transitions from the Ga-O levels, while that of green-yellow band was attributed to radiative transitions from oxygen vacancies. Particularly, the sample synthesized with Gallium acetylacetone precursor presented the highest phosphorescent emission intensity and had a CIE coordinates of (x = 0.27, y = 0.33), which is close to that for pure white light (x = 0.33, y = 0.33). Since the ZGO presented a white phosphorescent emission without doping with rare earths, they could be good candidates for lighting or signaling applications.

A facile route for highly efficient color-tunable Cu-Ga-Se/ZnSe quantum dots

I-III-VI group “green” quantum dots (QDs) are receiving increasing attention in photoelectronic conversion applications. In this work, a facile one-pot route directly dissolving copper iodide, gallium acetylacetonate and selenium powder as precursors into a mixed solution of dodecanethiol, oleylamine (OLA) and octadecene was developed to synthesize Cu-Ga-Se/ZnSe (CGSe/ZnSe) core/shell QDs. The resulting CGSe/ZnSe QDs with a relatively high photoluminescence quantum yield (PL QY) of 77.73% can be obtained and the particle size control from 4.20 to 5.73 nm can be realized via the variation of OLA dosage. The tunable emission from 485 to 630 nm can be acquired by introducing sulfur ion into CGSe host materials (anionic alloying) and varying the Cu/Ga precursor molar ratio. Furthermore, the PL recombination process in CGSe/ZnSe QDs is discussed using the PL decay curve. The proposed one-pot synthesis route for highly efficient color-tunable CGSe/ZnSe QDs is facile, rapid and environmentally-friendly. The as-prepared QDs are promising candidates for the exploration of novel and efficient light-emitting diodes.

In situ induced core/shell stabilized hybrid perovskites via gallium(iii) acetylacetonate intermediate towards highly efficient and stable solar cells

Introduction of gallium(iii) acetylacetonate (GaAA3) induced CsxFA1−xPbI3–[GaAA3]4 (0 &lt; x &lt; 1) core–shell hybrid-materials based perovskite solar cell with remarkably high stability.

High-Performance Solution-Processed Amorphous InGaZnO Thin Film Transistors with a Metal–Organic Decomposition Method

A facile solution process was introduced for the preparation of IGZO thin films via a metal–organic decomposition (MOD) method. The IGZO ink was synthesized by mixing the solutions of gallium acetylacetonate [Ga(C5H7O2)3], zinc acetylacetonate hydrate [Zn(C5H7O2)2·xH2O] dissolved in ethanol, and indium acetylacetonate [In(C5H7O2)3] dissolved in tetrahydrofuran (THF). The deposited films by spin-coating were annealed at moderate process temperature (≤500°C). The relationship between device performance and postannealing temperature was studied. The result demonstrated that mobility of IGZO TFT increased as the annealing temperature increased. Based on the analysis of O 1s statement, the annealing temperature can influence the number of oxygen vacancy to further affect the carrier centration. In addition, the IGZO TFT devices with various Ga molar ratios were compared to demonstrate the influence of the Ga addition. The result demonstrated that the saturated mobilities (μe) decreased and VTH shifted to positive voltage as the Ga molar ratio was increased. It is likely that Ga can offer stronger chemical bonds between metal and oxygen that reduced the concentration of free carriers and thus help reducing VTH. As a result, the optimized performance of IGZO TFT with the mobility of 3.4 cm2V−1s−1 showed the MOD process was a promising approach.