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At least 19 records

In Situ deposition of YBCO high-T(sub c) superconducting thin films by MOCVD and PE-MOCVD

Metalorganic Chemical Vapor Deposition (MOCVD) offers the advantages of a high degree of compositional control, adaptability for large scale production, and the potential for low temperature fabrication. The capability of operating at high oxygen partial pressure is particularly suitable for in situ formation of high temperature superconducting (HTSC) films. Yttrium barium copper oxide (YBCO) thin films having a sharp zero-resistance transition with T( sub c) greater than 90 K and Jc approx. 10 to the 4th power A on YSZ have been prepared, in situ, at a substrate temperature of about 800 C. Moreover, the ability to form oxide films at low temperature is very desirable for device applications of HTSC materials. Such a process would permit the deposition of high quality HTSC films with a smooth surface on a variety of substrates. Highly c-axis oriented, dense, scratch resistant, superconducting YBCO thin films with mirror-like surfaces have been prepared, in situ, at a reduced substrate temperature as low as 570 C by a remote microwave-plasma enhanced metalorganic chemical vapor deposition (PE-MOCVD) process. Nitrous oxide was used as a reactant gas to generate active oxidizing species. This process, for the first time, allows the formation of YBCO thin films with the orthorhombic superconducting phase in the as-deposited state. The as-deposited films grown by PE-MOCVD show attainment of zero resistance at 72 K with a transition width of about 5 K. MOCVD was carried out in a commercial production scale reactor with the capability of uniform deposition over 100 sq cm per growth run. Preliminary results indicate that PE-MOCVD is a very attractive thin film deposition process for superconducting device technology.

Zhao, J.↗

In-situ deposition of YBCO high-Tc superconducting thin films by MOCVD and PE-MOCVD

Metal-Organic Chemical Vapor Deposition (MOCVD) offers the advantages of a high degree of compositional control, adaptability for large scale production, and the potential for low temperature fabrication. The capability of operating at high oxygen partial pressure is particularly suitable for in situ formation of high temperature superconducting (HTSC) films. Yttrium barium copper oxide (YBCO) thin films having a sharp zero-resistance transition with T(sub c) greater than 90 K and J(sub c) of approximately 10(exp 4) A on YSZ have been prepared, in situ, at a substrate temperature of about 800 C. Moreover, the ability to form oxide films at low temperature is very desirable for device applications of HTSC materials. Such a process would permit the deposition of high quality HTSC films with a smooth surface on a variety of substrates. Highly c-axis oriented, dense, scratch resistant, superconducting YBCO thin films with mirror-like surfaces have been prepared, in situ, at a reduced substrate temperature as low as 570 C by a remote microwave-plasma enhanced metal-organic chemical vapor deposition (PE-MOCVD) process. Nitrous oxide was used as a reactant gas to generate active oxidizing species. This process, for the first time, allows the formation of YBCO thin films with the orthorhombic superconducting phase in the as-deposited state. The as-deposited films grown by PE-MOCVD show attainment of zero resistance at 72 K with a transition width of about 5 K. MOCVD was carried out in a commercial production scale reactor with the capability of uniform deposition over 100 sq cm per growth run. Preliminary results indicate that PE-MOCVD is a very attractive thin film deposition process for superconducting device technology.

Zhao, J.↗

Investigation of carbon incorporation in laser-assisted MOCVD of GaN

Background carbon (C) impurity incorporation in metalorganic chemical vapor deposition (MOCVD) grown gallium nitride (GaN) represents one of the major issues in further improving GaN vertical power device performance. This work presents a laser-assisted MOCVD (LA-MOCVD) technique to address the high-C issue in MOCVD homoepitaxial GaN under different growth rate (Rg) regimes and studies the correlations between [C] and Rg. [C] in LA-MOCVD GaN is reduced by 50%–90% as compared to the conventional MOCVD GaN for a wide growth rate range between 1 and 16 μm/h. A mass-transport based model is developed to understand the C incorporation at different Rg regimes. The results obtained from the developed model are in good agreement with experimental data. The model further reveals that LA-MOCVD effectively suppresses C incorporation by reducing the active C species in the gas phase. Moreover, high step velocity in step flow growth mode can facilitate C incorporation at fast Rg, exhibiting steeper C increase. The theoretical model indicates that [C] can be suppressed below 1016 cm−3 with a fast growth rate (Rg) of 10 μm/h by utilizing higher power LA-MOCVD and freestanding GaN substrates with larger off-cut angles.

Physics↗

GaN MOCVD Growth on Native substrates for High Voltage (15-20 KV) Vertical Power Devices

This project aims to develop metalorganic chemical vapor deposition (MOCVD) homoepitaxy of GaN on native substrates with fast growth rate (15-20 μm/hr), low background doping (low-10 15 cm -3 ) and smooth surface morphology via comprehensive understanding of the crystal growth process including high quality GaN substrate development and surface preparation, impurity and native defects control, and their impacts on the breakdown field. The team successfully developed a new growth process by introducing the laser-assisted MOCVD (LA-MOCVD) process to address the limited growth rates of GaN in the traditional MOCVD process. Specifically, the use of the CO2 laser with lasing wavelength of 9.219 μm, the strong coupling between the laser beam with the ammonia (GaN MOCVD precursor) leads to efficient decomposition of NH3 which significantly increases the effective group V/III molar ratio and thus suppresses C impurity incorporation in MOCVD GaN. The reduction in C incorporation in LA-MOCVD GaN is especially prominent when the GaN growth rate is fast (> 10 μm/hr), which allows to develop thick GaN films with high crystalline quality and low controllable doping needed for vertical high power device applications. The results of this project lead to the demonstration of vertical GaN PN diodes with record breakdown voltage of ~ 8kV with high Baliga’s figure of merit.

24 POWER TRANSMISSION AND DISTRIBUTION↗

High critical current STAR ® wires with REBCO tapes by advanced MOCVD

RE–Ba–Cu–O (REBCO, RE = rare earth) symmetric tape round (STAR ® ) wires of 1.5–2.5 mm diameter have been fabricated with 4–12 strands of symmetric REBCO tape made by advanced metal organic chemical vapor deposition (MOCVD). 1.5 mm diameter STAR ® wires made with just four advanced MOCVD tape strands are able to sustain nearly the same critical current (I c ) as 2.5 mm diameter wires made with 12 commercial-grade tape strands. An I c of 1070 A, corresponding to an engineering current density (J e ) of 597 A mm –2 , has been demonstrated at 4.2 K, 30 T in 1.5 mm diameter, four-strand wire at a bend radius of 15 mm. This I c value exactly matches the Ic expected from the lift factor of the tape strands used in the wire. The 2.5 mm diameter STAR ® wires made with 12 advanced MOCVD tape strands exhibit an I c of 1075 A at 77 K, self-field and sustained currents of 2500–2750 A at 4.2 K, 30 T before burnout, corresponding to a J e greater than 500 A mm –2 . Finally, these results show that the cost of STAR ® wires can be substantially reduced using fewer tape strands of high-performance advanced MOCVD tapes and that the superior bend performance of STAR ® wires can be maintained, even using 12 strands of advanced MOCVD tapes with 4 μm thick REBCO films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Trap characterization of high-growth-rate laser-assisted MOCVD GaN

A detailed study comparing defect incorporation between laser-assisted metal-organic chemical vapor deposition (MOCVD)-grown GaN and conventional low- and high-growth-rate MOCVD GaN was conducted. Using deep-level transient and optical spectroscopy, traps throughout the bandgap were characterized where traps were found at EC-0.25 eV, EC-0.57 eV, EC-0.72 eV, EC-0.9 eV, EC-1.35 eV, EC-2.6 eV, and EC-3.28 eV in all three samples. This indicates no new traps were observed in the laser-assisted MOCVD GaN sample. Overall, the trap concentrations in the laser-assisted MOCVD sample were ∼2× higher than the optimal low-growth-rate sample, but this is primarily due to the increase in gallium vacancy EC-2.6 eV and carbon-related EC-3.28 eV trap concentrations. The EC-0.9 eV trap concentration was ∼2× higher in the laser-assisted sample, so proton irradiation experiments were conducted to identify the physical source of this level. The results indicated this was a native point defect likely related to gallium interstitials. Overall, this study shows that the laser-assisted MOCVD growth method is promising for future thick, high-quality GaN epilayers after further growth optimizations.

Physics↗

Scale Up of High-Performance REBCO Tapes in a Pilot-Scale Advanced MOCVD Tool With In-Line 2D-XRD System

We have reported the development of an Advanced Metal-Organic Chemical Vapor Deposition (AMOCVD) method featuring ohmic heating of the substrate for REBCO film growth, direct tape temperature monitoring, and laminar precursor flow. This A-MOCVD method has been used to fabricate 4 – 5 m thick film REBCO tapes with record high performance: critical currents exceeding 8700 A/12 mm at 30 K, 3 T; and engineering current density of 5200 A/mm 2 at 4.2 K, 15 T. Recently, we constructed a pilot-scale reel-to-reel A-MOCVD system to scale up the technology to long tapes. Preliminary batches of tapes exhibit consistent performance and good uniformity along the length. An in-line 2D X-ray Diffraction (XRD) system has been integrated into the pilot A-MOCVD tool to monitor the REBCO texture and composition, RE 2 O 3 content, and the dimensions of BaMO 3 (BMO, M=Zr,Hf) nanorods that act as artificial pinning centers. Specifically, the streaking angle between REBCO (103) and BZO (101) has been found to correlate well with (Ba+M)/Cu of the film, lift factor in critical current over a range of temperatures and magnetic fields, and the size of the BMO nanorods. Furthermore, the in-line 2D-XRD is expected to serve as a valuable quality measuring tool supporting realtime feedback control for the process to yield uniform and consistent manufacturing of high performance REBCO tapes by Advanced MOCVD.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Radiation effects on p+n InP junctions grown by MOCVD

The superior radiation resistance of InP over other solar cell materials such as Si or GaAs has prompted the development of InP cells for space applications. The early research on radiation effects in InP was performed by Yamaguchi and co-workers who showed that, in diffused p-InP junctions, radiation-induced defects were readily annealed both thermally and by injection, which was accompanied by significant cell recovery. More recent research efforts have been made using p-InP grown by metalorganic chemical vapor deposition (MOCVD). While similar deep level transient spectroscopy (DLTS) results were found for radiation induced defects in these cells and in diffused junctions, significant differences existed in the annealing characteristics. After injection annealing at room temperature, Yamaguchi noticed an almost complete recovery of the photovoltaic parameters, while the MOCVD samples showed only minimal annealing. In searching for an explanation of the different annealing behavior of diffused junctions and those grown by MOCVD, several possibilities have been considered. One possibility is the difference in the emitter structure. The diffused junctions have S-doped graded emitters with widths of approximately 0.3 micrometers, while the MOCVD emitters are often doped with Si and have widths of approximately 300A (0.03 micrometers). The difference in the emitter thickness can have important effects, e.g. a larger fraction of the total photocurrent is generated in the n-type material for thicker emitters. Therefore the properties of the n-InP material may explain the difference in the observed overall annealing behavior of the cells.

Messenger, Scott R.↗

Growth of High-Performance 4-5μm Thick Film REBCO Tapes Doped With Hafnium Using Advanced MOCVD

Advanced metal organic chemical vapor deposition technique (A-MOCVD) was used to grow 4-5 µm thick REBa 2 Cu 3 O 7–δ (REBCO, RE = rare earth) films, doped with 5% and 15% Hf. Thick REBCO films doped with 5% Hf exhibit self-field critical current density (J c ) over 1.8 MA/cm 2 at 77 K and 3 MA/cm 2 at 65 K, 1.5 T. Increasing the Hf content to 15% resulted in J c above 9 MA/cm 2 at 20 K, 9 T. The effect of (Ba+Hf)/Cu content in Hf-added (5 and 15 mol.%) REBCO films on the critical current density at 77 K, 0 T, c-axis lattice parameter and out-of- plane texture has been studied. In addition to growth of thick film REBCO tapes with superior performance, the A-MOCVD reactor has been used to quadruple the precursor-to-film conversion efficiency above 45%. Furthermore, this achievement has a first order impact in lowering the cost of REBCO tapes made by A-MOCVD.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Correlations Between In-Line X-ray Diffraction Data and In-Field Critical Current of Long, 4-μm Thick Film REBCO Tapes Made by Advanced MOCVD

REBa 2 Cu 3 O 7-δ (REBCO, RE = rare earth) tapes with high critical current can be very impactful in high magnetic field applications at low temperatures and power applications at high temperatures. A pilot-scale Advanced Metal Organic Chemical Vapor Deposition (MOCVD) method was used to fabricate 50-m-long, 4+μm-thick REBCO tape in a single pass. Critical currents 3.3x that of commercial HTS tapes were achieved at 20 K, 12 T in these 50-m-long tapes. An in-line 2D X-ray Diffraction (XRD) system has been used to assess the quality of the long tapes in real-time, during manufacturing. The key peaks of REBCO, REO, and BZO phases were identified and utilized for tape quality analysis. Furthermore, a 20-m tape made by Advanced MOCVD was tested over its entire length by reel-to-reel (R2R) scanning Hall-probe microscopy (SHPM) at 65 K, 0.25 T, 2 T, and 4 T. 4-mm-wide strands of Advanced MOCVD tapes showed mean critical currents at 65 K of 530 A, 200 A, and 104 A at 0.25 T, 2 T, and 4 T respectively. The combined use of in-line and offline characterization techniques provides a reliable approach for assessing long REBCO tapes during manufacturing, serving as an effective feedback source for quality control in scaled-up REBCO tape deposition processes. This advancement contributes to the production of longer and more uniform high-performance REBCO tapes for large-scale, high-field superconducting applications

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing unintentional Fe impurity incorporation in MOCVD homoepitaxy GaN: Toward GaN vertical power devices

Unintentional impurity incorporation in GaN drift layers represents a challenging issue that can limit their potential performance in vertical power devices. In this paper, we focus on studying the origins of Fe impurity incorporation in metal-organic chemical vapor deposition (MOCVD) grown GaN materials. Acting as a compensator in n-type GaN drift layers, Fe impurities can reduce the electron mobility in GaN and limit the lowest controllable doping level. Two sources, the sample cleaning process and growth susceptor, were identified as the main mechanisms of Fe incorporation in the MOCVD GaN growth process. It was found that solvent cleaning of the wafer can introduce significant Fe contamination at the growth interface, which would slowly be incorporated into the GaN epilayer, thus causing background Fe impurity as high as 10 17 cm -3 level. Moreover, the Fe impurity in the coating material on the susceptor can introduce additional Fe impurity during the growth process. Our studies revealed that the Fe impurity level could be significantly suppressed by more than two orders when an alternative cleaning process was used and the susceptor surface was fully covered by substrates. Characterization of the Fe impurity concentrations was performed via secondary ion mass spectrometry. The trap level (E C - 0.57) eV from deep-level transient spectroscopy that had previously been attributed to Fe confirmed the carrier compensation effect from Fe. Room temperature Hall mobility as high as 1007 cm 2 /V s was achieved on the MOCVD grown low-Fe GaN. Results from this work will provide guidance for achieving high purity GaN toward high performance GaN vertical power devices.

42 ENGINEERING↗

Safety-Enclosure System For MOCVD Process Chamber

Safety-enclosure system filled with nitrogen surrounds reaction chamber in which metallo-organic chemical vapor deposition (MOCVD) performed. Designed to protect against explosions and/or escaping toxic gases and particulates. Gas-purification subsystem ensures during loading and unloading of process materials, interior of MOCVD chamber exposed to less than 1 ppm of oxygen and less than 5 ppm of water in nitrogen atmosphere. Toxic byproducts of MOCVD process collected within inert atmosphere. Enclosure strong enough to contain any fragments in unlikely event of explosion.

Singletery, James, Jr.↗

40-meter-long REBCO tapes with critical current over 4,000 A/12 mm at 4.2 K and 13 T by advanced MOCVD

REBa 2 Cu 3 O 7–δ (REBCO, RE = rare earth) tapes doped with 5% and 15% Zr have been scaled up to lengths more than 40 m in a pilot-scale advanced metal organic chemical vapor deposition (A-MOCVD) tool. The precursor compositions used for the long tapes were guided by a study of the influence of (Ba + dopant)/Cu content on the critical current density (J c ) of 5 and 15 mol.% Hf- and Zr-added tapes at 4.2 K and 13 T. The 40-m-long tapes exhibited a critical current (I c ) over 4,000 A/12 mm at 4.2 K and 13 T as well as over 1,400 A/12 mm at 20 K and 20 T. The critical current densities of a 40-m-long tape doped with 5% Zr at 4.2 K measured at the National High Magnetic Field Laboratory (NHMFL) were > 10 MAcm –2 and >5 MAcm –2 at 14 T and 30 T, respectively, which are over three times those of commercial REBCO tapes. The infield J c of 5% Zr-added 40-m-long tapes was similar to those of previously-reported high-performance short samples made with 15% Zr or Hf. These results demonstrate the excellent potential of A-MOCVD for manufacturing high I c REBCO tapes for use in ultrahigh-field magnet applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

All-MOCVD-grown gallium nitride diodes with ultra-low resistance tunnel junctions

In this work, we carefully investigate three important effects including postgrowth activation annealing, delta (δ) dose and magnesium (Mg) buildup delay as well as experimentally demonstrate their influence on the electrical properties of GaN homojunction p–n diodes with a tunnel junction (TJ). The diodes were monolithically grown by metalorganic chemical vapor deposition (MOCVD) in a single growth step. By optimizing the annealing parameters for Mg activation, δ-dose for both donors and acceptors at TJ interfaces, and p + -GaN layer thickness, a significant improvement in tunneling properties is achieved. For the TJs embedded within the continuously-grown, all-MOCVD GaN diode structures, ultra-low voltage penalties of 158 mV and 490 mV are obtained at current densities of 20 A cm –2 and 100 A cm –2 , respectively. The diodes with the engineered TJs show a record-low differential resistivity of 1.6 × 10 –4 Ω cm 2 at 5 kA cm –2 .

42 ENGINEERING↗

MOCVD Growth and Characterization of ZnSnN 2

Since the first few reports of its synthesis in 2011 and 20121-3, interest in ZnSnN 2 for diverse applications, including photovoltaics1,3,4, visible light photocatalysis5, and optoelectronics, has been growing. Novel nitride-based LED device designs promise high gains in efficiency at emission wavelengths into the green, amber and even red.6-8 Their realization requires the precise insertion of an ultrathin layer of ZnGeN 2 or ZnSnN 2 into the active region of an InGaAs-GaAs LED structure. While thin films of ZnSnN 2 have been synthesized by RF sputtering1,9 and by MBE 2,10,11, and thin films of ZnGeN 2 , ZnSiN 2 and their alloys by MOCVD, the synthesis of ZnSnN 2 thin films by MOCVD has not yet been reported. It is a challenging goal, given the narrow temperature window between efficient activation of ammonia and the thermal decomposition of ZnSnN 2 at near-atmospheric pressures. We report here the results of studies of ZnSnN 2 films grown on r- and c-plane sapphire substrates, GaN templates on sapphire, and In 0.15 Ga 0.85 N templates on GaN-on-sapphire, at temperatures from 500 °C to 560 °C, using tetramethyltin (TMSn), diethylzinc (DEZn), germane and ammonia. Chamber pressures were varied between 200 and 500 torr. In addition, the ratios of the cation precursors and the total cation-to-anion precursor ratios were varied. Single crystal growth, as evidenced by 2θ-ω x-ray diffraction scans, was achieved on all of these substrates. Wurtzitic (0002) ZnSnN 2 diffraction were observed at 2θ ~ 32.90 for the samples grown on c-sapphire, GaN (0001) and InGaN (0001) templates, and wurtzitic (11-20) peak at 2θ ~ 54.80 for the films grown on r-sapphire. Higher pressures and higher temperatures promoted better crystallinity and more continuous films, as revealed by scanning electron microscopy (SEM) images and 2θ-ω x-ray diffraction peak widths and intensities. Crystal quality was observed to be highly dependent on growth temperature. For example, in one series a 10 °C change in growth temperature resulting in a factor of 15 increase in diffraction peak intensity. SEM images show that films grown on the GaN templates had better uniformity in nucleation than those grown on sapphire. The presence of satellite peaks around the Bragg peak in the XRD 2θ-ω scan for a film grown on a GaN template, and the absence of satellite peaks for the films grown simultaneously on c- and r-sapphire, also indicate superior quality for the film grown on GaN. HAADF-STEM images of films grown on these templates showed smooth interfaces at the film-substrate boundary and show growth rates as high as 167 nm/h, considerably higher than reported previously for MBE growth.9,10 Electron diffraction patterns show single crystallinity. Rocking curves show FWHM as low as 0.100. RMS surfaces roughnesses, measured by atomic force microscopy, are of the order of 3 nm for 1µm x 1µm areas. Current work is focusing on optimizing growth on InGaN templates. These templates are promising for their relatively lower lattice mismatch with ZnSnN 2 . Their use is a next step toward producing LED device structures.

Jayatunga, Benthara Hewage Dinushi↗

Development of Metal Boride/Carbide Precursors for MOCVD Applications

This report describes the proposed efforts for a three-year (CY23-25) program to develop refractory metal boride/carbide precursors for metal-organic chemical vapor deposition (MOCVD) applications. Reported are the CY24 results on the thermal processing of bis-cyclopentadienyl dialkyl and tetra-alkyl precursors to obtain metal carbide products. Precursors evaluated are commercially available. Materials were processed within in a custom-built MOCVD system at 1000 ⁰C, as well as in a hot isostatic press (HIP) at temperatures of 1000 ⁰C or 1650 ⁰C at pressures of 5000 psi. The products were identified as metal carbide, metal oxide, or a mixture of carbide and oxide phases depending on the starting material and process used. Density functional theory calculations were performed to determine the decomposition mechanism and to inform how ligand choice led to the products.

36 MATERIALS SCIENCE↗

Bandgap Engineering of Ga 2 O 3 by MOCVD Through Alloying with Indium

Ga 2 O 3 and In 2 O 3 are vital semiconductors with current and future electronic device applications. Here, we study the alloying of In 2 O 3 and Ga 2 O 3 (IGO) and the associated changes in structure, morphology, band gap, and electrical transport properties. Undoped films of IGO were deposited on sapphire substrates with varying indium (In) percentage from zero to 100% by metal-organic chemical vapor deposition (MOCVD). Some films were annealed in H 2 to induce electrical conductivity. The measurements showed the optical band gap decreased by adding In; this was confirmed by density functional (DFT) calculations, which revealed that the nature of the valence band maximum and conduction band minimum strongly relate to the chemistry and that the band gap drops by adding In. The as-grown films were highly resistive except for pure In 2 O 3 , which possesses p-type conductivity, likely arising from In vacancy-related acceptor states. N-type conductivity was induced in all films after H-anneal. DFT calculations revealed that the presence of In decreases the electron effective mass, which is consistent with the electrical transport measurements that showed higher electron mobility for higher In percentage. The work revealed the successful band gap engineering of IGO and the modification of its band structure while maintaining high-quality films by MOCVD.

36 MATERIALS SCIENCE↗