The X-Ray Diffraction Method for Study of Growth Defects in CVD Diamond Single Crystals
X-ray diffraction from Chemical Vapor Deposition (CVD) gem-quality colorless diamond single crystals, grown with nitrogen addition in methane –hydrogen plasma mixture, was studied by imaging plate area detector (IPD) giving pixel pattern. Growth defects are responsible for rising x-ray diffuse scattering beyond reciprocal lattice points (rlp), described in the framework of kinematical theory of X-ray diffraction. In the particular case of CVD diamond crystals grown epitaxially on (001) substrate, the additional scattering in the close vicinity of rpl’s was registered. This observation was possible because of the improved angular resolution of x-ray intensity measurements using imaging plate detector (IPD). The pronounced differences in scattering around 111 rlp’s for natural and CVD <001> growth sector were demonstrated. Oscillation and stationary crystal methods allowed registration of diffraction spots that are different from natural diamond crystals. The diffraction patterns include features of short- and long-range atomic order. There are satellite reflections at the positions corresponding to the interatomic distances at 1.51 Å and 1.57 Å in the vicinity of 111 Bragg reflections, which are characteristic to 1.54 Å of cubic diamond. The displacement disorder of atoms, understood as disturbance of lattice periodicity can be explained by hypothesis about linear defects running in <110> and <-110> directions. Along <110> twin line tetrahedra share edges. Hydrogen atoms are presumably incorporated along this linear twin to protect chemical bonding stability. Bragg reflections exhibit anisotropy and considerable broadening compared to the diffraction standards. The ratio of peak intensity of forbidden by the diamond space group symmetry 222 reflection to 111 reflection is larger than for natural crystal. Raman spectra from (001) CVD crystals fit well to the spectrum from nearly perfect natural diamond crystal. The X-ray scattering around Bragg reflection is characteristic for a given crystal and can be applied as a gem quality criterion for distinguishing among crystals of different origin, or different growth sectors or grown by different methods. The scattering around 111 CVD diamond reflection is the strongest among the rlp’s.
The X-Ray Diffraction Method for Study of Growth Defects in CVD Diamond Single Crystals, Advances in Materials.
Vol. 7, No. 4,
2018, pp. 89-104.
Badzian, A. The displacement disorder of atoms in diamond crystals revealed by x-ray imaging plate detector, Diamond and Related Materials 2016, 69, 19-32
Mierzejewska, S., Niemyski, T., J. Less-Common Metals 1966, 10, 33-37
Badzian, A; Niemyski, T.; Appenheimer, S.; Olkusnik, E. “Graphite-Boron Nitride Solid Solutions” in F. A. Glaski, (Ed.), Proceedings of the Third International Conference on Chemical Vapor Deposition, Salt Lake City, April 24-27.
Badzian, A., Cubic boron nitride – diamond mixed crystals (soild solutions), Materials Research Bulletin 1981, 16,1385-1393
Badzian, A., Badzian, T., Lee, S.-Tong Synthesis of diamond from methane and nitrogen mixture, Appl. Phys. Lett. 1993, 62, 3432-3434
Badzian, A., Recent developments in hard materials, Refractory Metals and Hard Materials, 1997 15, 3-12
Badzian, A.; Badzian, T. Perpendicularly stacked graphite nanotubes, Carbon, 2000, 38, 1507-9.
Locher, R, C. Wild, N, Herres, D. Beher, P. Koidl, Nitrogen stabilized <100> texture in chemical vapor deposition diamond films, Appl. Phys. Lett. 65, 1994, 34 – 36.
Pickrell, D., R. Messier, R. E. W. Zhu, A. Badzian, R. Newnham “Downstream plasma-enhanced diamond film deposition, Appl. Phys. Lett. 56, 1990, 2010-2012.
Ziminsky, P. How high quality synthetic diamonds will impact the market, Kitco Contributed Commentaries, Web page, July 12,2013
Zhao, X-Z; Roy, K; Cherian, K. A; Badzian, A. Hydrothermal growth of diamond in metal-C-H2O systems, Nature 1997, 385, 513-515.
Badzian, A; Badzian, T. Diamond homoepitaxy by chemical vapor deposition, Diamond and Related Materials 1992, 2, 147-157.
Badzian, A.; Badzian, T.; Wang, X. H.; Hartnett, T. M. Growth Sectors of CVD Diamond, New Diamond Science and Technology, Materials Research Society: Pittsburg, Pennsylvania, 1991, pp.549-556.
Badzian, A.; Badzian, T. Defects in CVD diamonds, Ceramic International, 1996, 22, 223-229.
Erni, R.; Freitag, B.; Hartel, P.; Muller, H.; Tiemeijer, P.; van der Stam, M; Stekelenburg, M; Hubert, D;Specht, P; Garibay-Febles, V. Atomic scale analysis of planar defects in polycrystaline diamond, Microsc Microanal. 2006, 12,492-7.
Badzian, A.; Badzian, T. An intermediate hybridization in diamond: edge-shared tetrahedra, Thin Solid Films 2004, 447-448, 163-168.
Lee, N. Microwave plasma-assisted chemical vapor deposition and characterization of (001) homoepitaxial diamond films, PhD Thesis, The Pennsylvania State University, May 1996.
Kuang, Y. Study of growth and nucleation of chemical vapor deposition diamond and amorphous silicon carbon alloy thin films, PhD Thesis, The Pennsylvania State University, May 1997.
Kuang, Y.; Wang, Y., Lee, N.; Badzian, A.; Badzian, T.; Tsong, T. T. Surface structure of homoepitaxial diamond (001) films, a scanning tunneling microscopy study, Appl. Phys. Lett. 1995, 67, 3721-3723.
Kuang, Y.; Lee, N.; Badzian, A.; Tsong, T. T.; Badzian, T.; Chen, Ch. Study of antiphase boundaries local 3x1 configuration on the (001) surface of homoepitaxial diamond films by scanning tunneling microscopy, Diamond and Related Materials, 1995, 4, 1371-1375.
Badzian A. Synthesis of diamond from the gas phase, Electric Refractory Materials: Marcel Decker, New York, NY, 2000, pp. 347-368.
Grot, S. A.; Gildenblat, G. Sh.; Hatfield, C. W.; Wronski, C. R.; Badzian, A.; Badzian, T.; Messier, R. The effect of surface treatment on electrical properties of metal contacts to boron-doped homoepitaxial diamond films, IEEE Electron Device Lett. 1990, 11, 100-102.
Stallcup, R. E.; Avies, A. F.; Perez, J. M. Atomic resolution ultrahigh vacuum scanning tunneling microscopy of epitaxial diamond (100) films, Appl. Phys. Lett. 1995, 66, 2331-2333.
Hutchison, J. L; Shechtman, D. High resolution electron microscopy of CVD diamond film, Advanced Materials ’94, International Communications Specialists, Inc.:Tokyo, 1994, pp. 152-156.