Kohei Shima, Haruto Tsujitani, Shigefusa F. Chichibu
{"title":"三(二甲氨基)硼烷金属有机化学气相沉积法制备sp2键合BN薄膜的深紫外发光","authors":"Kohei Shima, Haruto Tsujitani, Shigefusa F. Chichibu","doi":"10.1016/j.jcrysgro.2025.128370","DOIUrl":null,"url":null,"abstract":"<div><div><em>sp</em><sup>2</sup>-bonded BN films exhibiting deep-ultraviolet luminescence peaks were grown by metalorganic chemical vapor deposition using tris(dimethylamino)borane [TDMAB, B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub>] and NH<sub>3</sub> as B and N sources, respectively. BN films with thicknesses ranging from 0.7 to 6.1 µm were grown at temperatures (<span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span>) between 1200 and 1500 °C, under mass-transport-limited growth conditions. The results of x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman-scattering spectroscopy, and x-ray photoelectron spectroscopy confirmed the dominance of turbostratic BN and the presence of partially ordered structures such as ABC-stacked rhombohedral phases, along with minor contributions from B-O and C-N bonds. The films exhibited broad cathodoluminescence bands centered at 5.5 eV, 4.1 eV, and 3.2 eV, which are attributable to stacking defects, most probably C impurities, and possibly O impurities, respectively. One of the samples exhibited distinct zero-phonon lines at 4.14 and 4.16 eV attributable to C dimer defects in ABC-stacked (rhombohedral) and AB-stacked (Bernal) BN phases, respectively. Compared with a reference BN epilayer grown using the BCl<sub>3</sub>-NH<sub>3</sub>-N<sub>2</sub> gas system, B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub>-grown films exhibited approximately twofold higher cathodoluminescence intensities in the 5.2–6.1 eV range at 300 K, likely due to the reduced incorporation of nonradiative recombination centers. The cathodoluminescence intensity was maximized at <span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span> = 1400 °C, while both higher and lower <span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span> resulted in higher concentrations of nonradiative recombination centers, likely associated with C-N bonds and divacancies comprising a B-vacancy and a N-vacancy, V<sub>B</sub>V<sub>N</sub>, respectively. These results demonstrate that B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub> is a suitable B source for the deposition of luminescent BN films, offering the potential for improved deep-ultraviolet emitter performance through reduced impurity incorporation.</div></div>","PeriodicalId":353,"journal":{"name":"Journal of Crystal Growth","volume":"672 ","pages":"Article 128370"},"PeriodicalIF":2.0000,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Deep-ultraviolet luminescence from sp2-bonded BN films grown by metalorganic chemical vapor deposition using tris(dimethylamino)borane\",\"authors\":\"Kohei Shima, Haruto Tsujitani, Shigefusa F. Chichibu\",\"doi\":\"10.1016/j.jcrysgro.2025.128370\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div><em>sp</em><sup>2</sup>-bonded BN films exhibiting deep-ultraviolet luminescence peaks were grown by metalorganic chemical vapor deposition using tris(dimethylamino)borane [TDMAB, B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub>] and NH<sub>3</sub> as B and N sources, respectively. BN films with thicknesses ranging from 0.7 to 6.1 µm were grown at temperatures (<span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span>) between 1200 and 1500 °C, under mass-transport-limited growth conditions. The results of x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman-scattering spectroscopy, and x-ray photoelectron spectroscopy confirmed the dominance of turbostratic BN and the presence of partially ordered structures such as ABC-stacked rhombohedral phases, along with minor contributions from B-O and C-N bonds. The films exhibited broad cathodoluminescence bands centered at 5.5 eV, 4.1 eV, and 3.2 eV, which are attributable to stacking defects, most probably C impurities, and possibly O impurities, respectively. One of the samples exhibited distinct zero-phonon lines at 4.14 and 4.16 eV attributable to C dimer defects in ABC-stacked (rhombohedral) and AB-stacked (Bernal) BN phases, respectively. Compared with a reference BN epilayer grown using the BCl<sub>3</sub>-NH<sub>3</sub>-N<sub>2</sub> gas system, B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub>-grown films exhibited approximately twofold higher cathodoluminescence intensities in the 5.2–6.1 eV range at 300 K, likely due to the reduced incorporation of nonradiative recombination centers. The cathodoluminescence intensity was maximized at <span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span> = 1400 °C, while both higher and lower <span><math><mrow><msub><mi>T</mi><mi>g</mi></msub></mrow></math></span> resulted in higher concentrations of nonradiative recombination centers, likely associated with C-N bonds and divacancies comprising a B-vacancy and a N-vacancy, V<sub>B</sub>V<sub>N</sub>, respectively. These results demonstrate that B[N(CH<sub>3</sub>)<sub>2</sub>]<sub>3</sub> is a suitable B source for the deposition of luminescent BN films, offering the potential for improved deep-ultraviolet emitter performance through reduced impurity incorporation.</div></div>\",\"PeriodicalId\":353,\"journal\":{\"name\":\"Journal of Crystal Growth\",\"volume\":\"672 \",\"pages\":\"Article 128370\"},\"PeriodicalIF\":2.0000,\"publicationDate\":\"2025-10-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Crystal Growth\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022024825003240\",\"RegionNum\":4,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CRYSTALLOGRAPHY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Crystal Growth","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022024825003240","RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CRYSTALLOGRAPHY","Score":null,"Total":0}
Deep-ultraviolet luminescence from sp2-bonded BN films grown by metalorganic chemical vapor deposition using tris(dimethylamino)borane
sp2-bonded BN films exhibiting deep-ultraviolet luminescence peaks were grown by metalorganic chemical vapor deposition using tris(dimethylamino)borane [TDMAB, B[N(CH3)2]3] and NH3 as B and N sources, respectively. BN films with thicknesses ranging from 0.7 to 6.1 µm were grown at temperatures () between 1200 and 1500 °C, under mass-transport-limited growth conditions. The results of x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, Raman-scattering spectroscopy, and x-ray photoelectron spectroscopy confirmed the dominance of turbostratic BN and the presence of partially ordered structures such as ABC-stacked rhombohedral phases, along with minor contributions from B-O and C-N bonds. The films exhibited broad cathodoluminescence bands centered at 5.5 eV, 4.1 eV, and 3.2 eV, which are attributable to stacking defects, most probably C impurities, and possibly O impurities, respectively. One of the samples exhibited distinct zero-phonon lines at 4.14 and 4.16 eV attributable to C dimer defects in ABC-stacked (rhombohedral) and AB-stacked (Bernal) BN phases, respectively. Compared with a reference BN epilayer grown using the BCl3-NH3-N2 gas system, B[N(CH3)2]3-grown films exhibited approximately twofold higher cathodoluminescence intensities in the 5.2–6.1 eV range at 300 K, likely due to the reduced incorporation of nonradiative recombination centers. The cathodoluminescence intensity was maximized at = 1400 °C, while both higher and lower resulted in higher concentrations of nonradiative recombination centers, likely associated with C-N bonds and divacancies comprising a B-vacancy and a N-vacancy, VBVN, respectively. These results demonstrate that B[N(CH3)2]3 is a suitable B source for the deposition of luminescent BN films, offering the potential for improved deep-ultraviolet emitter performance through reduced impurity incorporation.
期刊介绍:
The journal offers a common reference and publication source for workers engaged in research on the experimental and theoretical aspects of crystal growth and its applications, e.g. in devices. Experimental and theoretical contributions are published in the following fields: theory of nucleation and growth, molecular kinetics and transport phenomena, crystallization in viscous media such as polymers and glasses; crystal growth of metals, minerals, semiconductors, superconductors, magnetics, inorganic, organic and biological substances in bulk or as thin films; molecular beam epitaxy, chemical vapor deposition, growth of III-V and II-VI and other semiconductors; characterization of single crystals by physical and chemical methods; apparatus, instrumentation and techniques for crystal growth, and purification methods; multilayer heterostructures and their characterisation with an emphasis on crystal growth and epitaxial aspects of electronic materials. A special feature of the journal is the periodic inclusion of proceedings of symposia and conferences on relevant aspects of crystal growth.