Epitaxy of boron phosphide on AIN, 4H-SiC, 3C-SiC and ZrB₂ substrates

Doctor of PhilosophyDepartment of Chemical EngineeringJames H. EdgarThe semiconductor boron phosphide (BP) has many outstanding features making it attractive for developing various electronic devices, including neutron detectors. In order to improve the efficiency of these devices, BP must have high crystal quality along with the best possible electrical properties. This research is focused on growing high quality crystalline BP films on a variety of superior substrates like AIN, 4H-SiC, 3C-SiC and ZrB₂ by chemical vapor deposition. In particular, the influence of various parameters such as temperature, reactant flow rates, and substrate type and its crystalline orientation on the properties of BP films were studied in detail. Twin-free BP films were produced by depositing on off-axis 4H-SiC(0001) substrate tilted 4° toward [1-100] and crystal symmetry matched zincblende 3C-SiC. BP crystalline quality improved at higher deposition temperature (1200°C) when deposited on AlN, 4H-SiC, whereas increased strain in 3C-SiC and increased boron segregation in ZrB₂ at higher temperatures limited the best deposition temperature to below 1200°C. In addition, higher flow ratios of PH₃ to B₂H₆ resulted in smoother films and improved quality of BP on all substrates. The FWHM of the Raman peak (6.1 cm⁻¹), XRD BP(111) peak FWHM (0.18°) and peak ratios of BP(111)/(200) = 5157 and BP(111)/(220) = 7226 measured on AlN/sapphire were the best values reported in the literature for BP epitaxial films. The undoped films on AlN/sapphire were n-type with a highest electron mobility of 37.8 cm²/V·s and a lowest carrier concentration of 3.15x1018 cm⁻ᶟ. Raman imaging had lower values of FWHM (4.8 cm⁻¹) and a standard deviation (0.56 cm⁻¹) for BP films on AlN/sapphire compared to 4H-SiC, 3C-SiC substrates. X-ray diffraction and Raman spectroscopy revealed residual tensile strain in BP on 4H-SiC, 3C-SiC, ZrB₂/4H-SiC, bulk AlN substrates while compressive strain was evident on AlN/sapphire and bulk ZrB₂ substrates. Among the substrates studied, AlN/sapphire proved to be the best choice for BP epitaxy, even though it did not eliminate rotational twinning in BP. The substrates investigated in this work were found to be viable for BP epitaxy and show promising potential for further enhancement of BP properties

CVD growth and properties of boron phosphide on 3C-SiC

Citation: CVD growth and properties of boron phosphide on 3C-SiC, B. Padavala, C.D.Frye, X. Wang, B. Raghothamachar, and J.H. Edgar, Journal of Crystal Growth, volume 449 pp. 15-21 (2016).Improving the crystalline quality of boron phosphide (BP) is essential for realizing its full potential in semiconductor device applications. In this study, 3C-SiC was tested as a substrate for BP epitaxy. BP films were grown on 3C-SiC(100)/Si, 3C-SiC(111)/Si, and 3C-SiC(111)/4H-SiC(0001) substrates in a horizontal chemical vapor deposition (CVD) system. Films were produced with good crystalline orientation and morphological features in the temperature range of 1000–1200 °C using a PH3+B2H6+H2 mixture. Rotational twinning was absent in the BP due to the crystal symmetry-matching with 3C-SiC. Confocal 3D Raman imaging of BP films revealed primarily uniform peak shift and peak widths across the scanned area, except at defects on the surface. Synchrotron white beam X-ray topography showed the epitaxial relationship between BP and 3C-SiC was (100)(100)〈011〉〈011〉BP||(100)(100)〈011〉〈011〉3C-SiC and (111)(111)View the MathML source〈112̅〉BP||(111)(111)View the MathML source〈112̅〉3C-SiC. Scanning electron microscopy, Raman spectroscopy and X-ray diffraction analysis indicated residual tensile strain in the films and improved crystalline quality at temperatures below 1200 °C. These results indicated that BP properties could be further enhanced by employing high quality bulk 3C-SiC or 3C-SiC epilayers on 4H-SiC substrates

Hydride CVD Hetero-epitaxy of B12P2 on 4 H-SiC

Icosahedral boron phosphide (B12P2) is a wide bandgap semiconductor (3.35 eV) that has been reported to “self-heal” from high-energy electron bombardment, making it attractive for potential use in radioisotope batteries, radiation detection, or in electronics in high radiation environments. This study focused on improving B12P2 hetero-epitaxial films by growing on 4 H-SiC substrates over the temperature range of 1250–1450 °C using B2H6 and PH3 precursors in a H2 carrier gas. XRD scans and Laue transmission photographs revealed that the epitaxial relationship was View the MathML source. The film morphology and crystallinity were investigated as a function of growth temperature and growth time. At 1250 °C, films tended to form rough, polycrystalline layers, but at 1300 and 1350 °C, films were continuous and comparatively smooth (View the MathML source). At 1400 or 1450 °C, the films grew in islands that coalesced as the films became thicker. Using XRD rocking curves to evaluate the crystal quality, 1300 °C was the optimum growth temperature tested. At 1300 °C, the rocking curve FWHM decreased with increasing film thickness from 1494 arcsec for a 1.1 μm thick film to 954 arcsec for a 2.7 μm thick film, suggesting a reduction in defects with thickness

Cubic boron phosphide epitaxy on zirconium diboride

Cubic boron phosphide (BP) is one of the least studied III-V compound semiconductors, in part because it is difficult to prepare in high quality form. In this study, zirconium diboride (ZrB2) was studied as a potential substrate for BP epitaxial layers, because of its advantages of a low lattice constant mismatch and high thermal stability. Two types of substrates were considered: ZrB2(0001) epitaxial films on 4H-SiC (0001) and bulk ZrB2(0001) single crystals. The optimal temperature for epitaxy on these substrates was 1100 degrees C; higher and lower temperatures resulted in polycrystalline films. The BP film/ZrB2 interface was abrupt as confirmed by cross-sectional transmission electron microscopy, attesting to the stability of ZrB2 under BP deposition conditions. The BP films were under compressive and tensile strain on ZrB2 and ZrB2/4H-SiC substrates, respectively, as determined by Raman spectroscopy, due to differences in the substrate/film coefficients of thermal expansion. This study suggests that with further optimization, ZrB2 can be an excellent substrate for BP epitaxial films. (C) 2017 Elsevier B.V. All rights reserved.Funding Agencies|Department of Energy [GEGF001846]; Swedish Research Council (VR) [621-2010-3921]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]</p

Epitaxy of Boron Phosphide on Aluminum Nitride(0001)/Sapphire Substrate

The boron phosphide (BP) semiconductor has many remarkable features, including high thermal neutron capture cross section of the ¹⁰B isotope, making it attractive for neutron detection applications. Effective and efficient neutron detection require BP to also have high crystal quality with optimum electrical properties. Here, we present the heteroepitaxial growth of high quality BP films on a superior aluminum nitride(0001)/sapphire substrate by chemical vapor deposition. The effect of process variables on crystalline and morphological properties of BP was examined in detail. BP deposited at high temperatures and high reactant flow rate ratios produced films with increased grain size and improved crystalline orientation. Narrower full width at half-maximum values of BP Raman peaks (6.1 cm^–1) and ω rocking curves (352 arcsec) compared to values in the literature confirm the high crystalline quality of produced films. The films were <i>n</i>-type with the highest electron mobility of 37.8 cm²/V·s and lowest carrier concentration of 3.15 × 10¹⁸ cm^–3. Rotational twinning in BP due to degenerate epitaxy caused by 3-fold BP(111) on 6-fold AlN(0001) was confirmed by synchrotron white beam X-ray topography. This preliminary study showed that AlN is an excellent substrate for growing high quality BP epitaxial films with promising potential for further enhancement of BP properties