Dr. Kuruvilla (Karl) Cherian Independent Materials Scientist-Consultant (Diamond and Advanced Materials Processing Technologies) Home Office: 347 Rose Brier Drive, Rochester Hills, Michigan, USA Email:
[email protected],
[email protected]
Excerpts from R&D work in:
Diamond Synthesis / Crystal Growth and Processing (at university and industrial laboratories in India, Australia and USA)
A. New Liquid Phase Route To Metastable Diamond Surface Crystallization B. HPHT Diamond Synthesis C. Diamond CVD D. Other Novel Approaches For Diamond And Related Materials Synthesis a) Solvo-Thermal Process For Diamond b) LPSSS Process: Plasma Assisted Metal-Carbon-Hydrogen Route To Diamond E. Decrystallization of Diamond by Nd:YAG and Excimer Lasers and Subsequent Lattice Relaxation F. Diamond Science & Technology Research Presentations And Papers At/In International Conferences And Research Publications
(If interested in similar projects, please contact:
[email protected])
Dr. K. Cherian-D-A1
A. New Liquid Phase Route To Metastable Diamond Surface Crystallization Doctoral and further research, at SPU in India and UQ in Australia. Ph.D. Thesis Title: THE DISSOLUTION AND METASTABLE AUTOEPITAXIAL RECRYSTALLIZATION OF DIAMOND* Research Supervisor: Professor A. R. Patel, Ph.D. (London), F.A.Sc., at Dept. of Physics (Solid State), SPU. (Former student of Professor S. Tolansky, F.R.S., D.Sc. at RHC, University of London) *This Ph.D. research showed for the first time ever, the possibility of diamond formation in a liquid phase under metastable conditions, by a dissolution and surface recrystallization process.
Media/News reports in: Diamond Depositions: Science & Technology (USA) vol.1, No.2, pp. 1, 31&32, 1990. Diamond Depositions: Science & Technology (USA) vol.2, No.6, pp. 1&9, 1991. Also cited in News & Views: Materials Science, Nature, Vol. 385, p. 485, Feb. 1997. Related Research reports in/at: Journal of Crystal Growth (Netherlands) 46 (1979) 706-708. Papers and Proceedings of the Seminar “The Many Facets of the Indian Diamond Industry”, Bombay, (1980) Paper C4. Indian Journal of Pure & Applied Physics, 19 (1981) 803-820. Pramana (Journal of Physics, Indian Academy of Sciencs) 22 (1984) 377-386. Current Trends in Crystal Growth and Characterization:, Proceedings of the IV National Seminar on Crystal Growth, University of Mysore; Ed. K. Byrappa (Publishers: MIT Associates Pvt. Ltd., Bangalore) (1991) 246-257. Surface and Coatings Technology (Netherlands) 47 (1991) 127-143. Applications of Diamond Films and Related Materials - Materials Science Monographs, 73 (1991) 389-394. Innovations in Materials Conference, Washington D.C., USA (July 1998)
Dr. K. Cherian-D-A2
Excerpts from the views and comments expressed by some of the leading scientists in the field of diamond research: 1. Professor J.C. Angus (Chemical Engineering Department, Case Western Reserve University, USA) “ …….. Your interpretation of the surface features as growth islands appears reasonable to me. However, I would be interested in learning a bit more about your experiments before I made anymore definite comments …….” (August 1977) “…… Your analysis of your observations seems entirely reasonable to me. As I mentioned in my earlier letter, I will be pleased to examine and comment on any manuscript you wish to submit for publication ……” (August 1978) 2. Dr. F. P. Bundy (G.E. C. Research & Development Center, New York, USA) “…… The photographs you enclosed are well-taken and very interesting ….. There could be some electrolytic action from the sides of the diamond exposed to the etchant and the side that is adjacent to the nickel crucible. This might account for the transport of some nickel to the diamond surface adjacent to it. There is a slight possibility that such electrochemical transport might involve carbon in some way that would allow deposition of atomic carbon on the diamond seed surface in a manner related to that claimed by Deryaguin and colleagues in Moscow …..” (January 1977) “…. If you truly have diamond overgrowths under the low pressure etching conditions it is a most remarkable phenomena” (March 1977) “….. If it is true there must be some driving force involving chemical potential, electrical potential, etc., and would deserve further careful scientific investigation to establish the mechanism…..” (June 1977) 3. Dr R.J. Caveney (Diamond Research Laboratory, Johannesburg, South Africa). “….. I was most interested to read your paper on metastable diamond growth – the results look scientifically very interesting …..” (October 1979) 4. Dr R. Diehl (Institut fur Angewandte Festkorperphysik, Federal Republic of Germany). “..... I have read with great interest your paper with Prof. Patel in the Journal of Crystal Growth; my congratulation for the very interesting results …..” (September 1980) 5. Professor T. Evans (J.J. Thomson Physical Laboratory, University of Reading, U.K.) “….I found your results of overgrowth on diamond very interesting and exciting… You have a very interesting problem and it should be studied further. It seems to be a very good technique for studying the kinetics and mode of growth”. (May 1978)
Dr. K. Cherian-D-A3
6. Professor Sir Charles Frank, O.B.E., F.R.S. (H.H. Wills Physics Laboratory, University of Bristol, U.K.) “….. It seems to me that it is most likely that the overgrowths on your diamonds are diamond. Nevertheless, there are always (rightly) people who are suspicious of any claim to have crystallized diamond ….. There is nothing incredible about crystallization of diamonds from a carbon-solvent under conditions of metastability relative to graphite….” (June 1978) Later after personally seeing the author’s experimental research results during a visit to India, Professor Sir Charles Frank writes: “Mr. Kuruvilla A. Cherian has been showing me some of his specimens and photographs… It appears to me that he has demonstrated another process in which metastable growth of diamond, at low pressure occurs. His idea seems reasonable to me, that this regrowth of diamond proceeds from “complexes” in solution…. This suggests the possibility of making a process, either by feeding in CO, or another carbon source (e.g. graphite) present for a while and then taken away again, whereby one could finish with a greater weight of diamond than one started with …..” (February 1980) 7. Dr. M. Moore (Royal Holloway College, University of London, U.K) “….. most interesting and worthy of publication …” 8. Dr. M. Seal (Amsterdam Diamond Test and Development Centre, D. Drukker & Zn. N.V., Amsterdam, Holland) “….. Your pictures are quite fascinating and I am inclined to think that the explanation of one new features which you put forward (metastable crystallization of diamond) may be the correct one…..” (Suggestions for some tests for positive identification also added) (August 1977) After conducting some tests on one of the author’s specimens with the overgrowths on it, at his laboratory, Dr. Seal writes: “….. I have checked the refractive index of these with immersion liquids and find it to be substantially greater than 1.74, the highest index liquid which we have here. Thus the refractive index (and indeed the general appearance) is consistent with the overgrowths being diamond. We are now doing some chemical tests and I shall inform you of results shortly”. (July 1978) “….. The sample was in fact exposed in 1978 to the chemical cleaning process (for diamonds) ….. with no apparent effect on the overgrowths. This strongly suggests that the overgrowths are diamond, but I shall try to confirm this now by treatment with molten salts. We have also checked by 2-beam white light Michelson interferometry with differential focusing that the features are in fact hills with heights in the range of several fringes. Of course, these tests only serve to confirm the tests you already did, but the sum total of the evidence leaves in my opinion little doubt that the overgrowths are diamond…..” (March 1980) “….. Further to my letter of March 18 this is to let you know that we treated your diamond with overgrowths in molten NaOH – NaNO3 (2 : 1 by weight ) at 500 0 600 C for 5 minutes with no apparent effect on the overgrowth. Thus the case for them being diamond is further strengthened. (March 1980) 9. Professor D. Tabor, F.R.S. (Cavendish Laboratory, University of Cambridge, U.K.) “….. I wish to say how interesting I found your letter and the results you described. If this effect is reproducible it would raise some very interesting practical possibilities ……” (July 1978) 10. Dr. E.M. Wilks (Clarendon Laboratory, University of Oxford, U.K.) “….. There is no doubt that if you have succeeded in forming new hillocks of diamond then that is a very important result…..” (May 1978)
Dr. K. Cherian-D-B1
B. HPHT Diamond Synthesis Process technology standardization at industrial plant in India. Media/News report in: Diamond Depositions: Science & Technology (USA) vol.2, No.7, p 6, 1991 Related Research reports in/at: Fifth International Conference on Surface Modification Technologies, University of Birmingham, U.K. (1991). III Annual General Meeting of the Materials Research Society of India, Indian Institute of Science, Bangalore, India (1992).
HP-HT cubic press - with WC cubic anvils
Graphite and Catalyst
Pyrophyllite cubes Accessories used in HP-HT diamond synthesis
Sections through the synthesis cells of different runs
Synthesized diamond grit embedded in the catalyst metal-carbon matrix; increasing diamond yield evident in samples from left to right.
Dr. K. Cherian-D-C1
C. Diamond CVD Establishment of a microwave plasma diamond CVD research facility and engineering diamond growth shapes, chemical processing of diamond, at University of Queensland Chemical Engineering Department in Australia Media/News report in: University of Queensland News: http://www.uq.edu.au/news/index.html?article=540 Related Research reports in/at: Diamond 1996: 7th European Conference on Diamond, Diamond-like & Related Materials and 5th International Conference on The New Diamond Science & Technology, Tours, France (September 1996). Chemeca ’98: 26th Australasian Chemical Engineering Conference, Port Douglas, Australia Diamond Materials IV - Proceedings of The 4th International Symposium on Diamond Materials, The Electrochemical Society, Proc. Vol. 95-4 (1995) 342-346. Applications of Diamond Films and Related Materials: Third International Conference, Feldman et.al., (eds), National Institute of Standards & Technology, USA (1995) 429432. Diamond for Electronic Applications, Materials Research Society Symposium Proceedings vol. 416 (1996) 241-247. Chemical Aspects of Electronic Ceramics Processing, Materials Research Society Symposium Proceedings vol. 495 (1997) 419-424 Diamond & Related Materials 9 (2000) 328-332
CVD Diamond Nucleation and Growth Characteristics
Engineered Diamond Growth Shapes
Dr. K. Cherian-D-D1
D. Other Novel Approaches For Diamond And Related Materials Synthesis At Penn State Materials Research Laboratory (Diamond Group), in the USA. D(a). Solvo-Thermal Process For Diamond Media/News reports in: Chemical & Engineering News, vol 75 (Feb 10, 1997) p.25 Nature 385, 485 (06 Feb 1997) News and Views
Related Research reports in/at: The 4th International Symposium on Diamond Materials, The Electrochemical Society, Reno, USA (May 1995). 3rd International Conference on Solvothermal Reactions Bordeaux, France (1999) Nature, 385 (1997) 513-515
D(b). LPSSS Process: Plasma Assisted Metal-Carbon-Hydrogen Route To Diamond Media/News reports in: Materials Technology 11 6-9, 1996 High-Tech Materials Alert (USA) vol. 12, No. 11, p.1, 1995 Related Research reports in/at: Materials Letters, 25 (1995) 191-193. Diamond Materials IV - Proceedings of The 4th International Symposium on Diamond Materials, The Electrochemical Society, Proc. Vol. 95-4 (1995) 95-99. Applications of Diamond Films and Related Materials: Third International Conference, Feldman et.al., (eds), National Institute of Standards & Technology, USA (1995) 391394. Diamond & Related Materials 6 (1997) 1747-1752 Keynote Paper at PacRim2: The 2nd International Meeting of Pacific Rim Ceramic Societies, Cairns, Australia, July 1996 Published in CD Rom, 1977 Materials Research Innovations, 1 (1997) 117-129
Starting material, poor morphology diamond grit ~15 micron size (left) Diamond growth in a Fe-C-H* liquid phase at ~ 1 atm.
Transformation of anhedral grit to cubooctahedral crystals ~30 micron size in about 4 hours through the Me-C-H processing approach (right)
Dr. K. Cherian-D-E1
E. Decrystallization of Diamond by Nd:YAG & Excimer Lasers and Subsequent Lattice Relaxation A new phenomenon was reported—decrystallization of a solid (diamond) by 1–5 eV photons, in a few seconds. A polycrystalline, 20 Å thick layer of CVD diamond on a WC substrate was exposed to two simultaneous pulsed laser beams 308 nm excimer, and 1.06 Am Nd:YAG in air ambient. The rough surface was ablated and smoothened, but the upper exposed half of the diamond layer was shown by Raman spectroscopy and X-ray diffraction to have been transformed to a non-crystalline phase. The 1332 cm1 Raman peak disappeared, demonstrating that lattice periodicity had been destroyed. Interestingly, the atomic disorder was gradually relaxed during five years at room temperature, and the Raman signature reappeared. The effect of decreasing intensity of diamond Raman peak has been demonstrated in single-crystal diamond. The distorted diamond lattice relaxed upon annealing in hydrogen plasma. The combination of pressure waves and the heating and cooling cycles is responsible for the creation and subsequent freezing of the atomic disorder, all in the solid state. The metastable states are introduced when atoms in the perfect lattice become displaced from the equilibrium positions. This is the process we term decrystallization—to distinguish it from glass formation, which requires the intermediary liquid state. With further development work, this may lead to a new color enhancement technology for some types of diamond. Fig. 1. Optical microscope image of diamond polycrystalline coating on the WC/Co cutting tool. The entire sample was illuminated by Nd:YAG laser, the left part was scanned by a line focused excimer laser beam perpendicular to the line of cut. The diamond film is transparent in the left part laser treated area and nontransparent in the right side. The lines seen in the left side correspond to the surface features of WC/Co tool existing before the diamond deposition.
Fig. 2. A comparison of Raman spectra taken on the top surface of diamond coating shown in Fig. 1. a) untreated and b) treated by excimer laser.
Fig. 3. Raman spectrum taken after 3 years, a) on the cross-section of untreated region, scale 10,000–20,000, b) on the cross-section of treated region 5 Å below the top surface scale 2000–8000, c) on the cross-section of treated region 3 Å below the top surface, scale 1000– 3000, d) on the cross-section of treated region 1 Å below the top surface, scale 400–1600, e) on the top surface of treated region, scale 400–800.
Dr. K. Cherian-D-F1
DR. KURUVILLA A. CHERIAN
F. Diamond Science & Technology Research Presentations And Papers At/In International Conferences and Research Publications Overgrowths on diamond at atmospheric pressure A.R. Patel and Kuruvilla A. Cherian, in: Journal of Crystal Growth (Netherlands) 46 (1979) 706-708. Growth of diamond at atmospheric pressure in a liquid medium A.R. Patel and Kuruvilla A. Cherian, in: Papers and Proceedings of the Seminar “The Many Facets of the Indian Diamond Industry”, Bombay, (1980) Paper C4. Crystallization of diamond at atmospheric pressure A.R. Patel and Kuruvilla A. Cherian, in: Indian Journal of Pure & Applied Physics, 19 (1981) 803-820. On the possible origins of natural diamonds A.R. Patel and Kuruvilla A. Cherian, in: Pramana (Journal of Physics, Indian Academy of Sciencs) 22 (1984) 377-386. The dissolution and metastable surface recrystallization of diamond: the possibility of a new method of diamond crystal growth Kuruvilla A. Cherian, in: Current Trends in Crystal Growth and Characterization:, Proceedings of the IV National Seminar on Crystal Growth, University of Mysore; Ed. K. Byrappa (Publishers: MIT Associates Pvt. Ltd., Bangalore) (1991) 246-257. Nickel-assisted metastable diamond formation (surface recrystallization) in a dissolution medium at atmospheric pressure Kuruvilla A. Cherian, in: Surface and Coatings Technology (Netherlands) 47 (1991) 127-143. Surface micromorphological characteristics of natural, HP-HT synthetic and metastably surface recrystallized diamond A.J. Kailath, M. Komath and K.A. Cherian, at: Fifth International Conference on Surface Modification Technologies, University of Birmingham, U.K. (1991). Metastable surface recrystallization of diamond from the liquid phase: substrate effects Kuruvilla A. Cherian, in: Applications of Diamond Films and Related Materials - Materials Science Monographs (USA), 73 (1991) 389-394. HP-HT synthesis of industrial diamonds Ansu J. Kailath and Kuruvilla A. Cherian, at: III Annual General Meeting of the Materials Research Society of India, Indian Institute of Science, Bangalore, India (1992). RF plasma assisted deposition of diamond-like carbon films from methanol-water vapour mixture Manoj Komath, Kuruvilla A. Cherian, S.A. Gangal and S.K. Kulkarni, at: IV Annual General Meeting of the Materials Research Society of India, Trivandrum, India (1993). Engineering diamond crystal shapes during combusion flame synthesis K.A. Cherian, J. Litster, V.Rudolph and E.T. White, in: Diamond Materials IV - Proceedings of The 4th International Symposium on Diamond Materials (USA), The Electrochemical Society, Proc. Vol. 95-4 (1995) 342-346. Evidence for slip and double spiral growth mechanism in combustion flame synthesized diamond. K.A. Cherian, J. Litster, V. Rudolph and E.T. White, in: Applications of Diamond Films and Related Materials - Third International Conference, Feldman et.al, (eds), National Institute of Standards & Technology, USA (1995) 429-432. Several approaches to diamond growth under hydrothermal conditions R.Roy, R.C. DeVries, D. Ravichandran, K.A. Cherian and A. Badzian, at: The 4th International Symposium on Diamond Materials, The Electrochemical Society, Reno, USA (May 1995). Single crystal and polycrystalline growth of diamond from metallic (MexCyHz) solutions below 1 atmosphere. Rustum Roy, H.S. Dewan, J.P. Cheng, K.A. Cherian and W.R. Drawl, in: Diamond Materials IV - Proceedings of The 4th International Symposium on Diamond Materials (USA), The Electrochemical Society, Proc. Vol. 95-4 (1995) 95-99. Diamond precipitation and single crystal homoepitaxial growth in the system Ag-C-H Rustum Roy, Jiping Cheng, William R. Drawl and Kuruvilla A. Cherian, in: Applications of Diamond Films and Related Materials: Third International Conference, Feldman et.al., (eds), National Institute of Standards & Technology, USA (1995) 391-394. Precipitation of diamond from metallic liquids below 1 atm. R. Roy, H.S. Dewan, K.A. Cherian, J.P. Cheng, A. Badzian, W. Drawl and C. Langlade, in: Materials Letters, 25 (1995) 191-193.
Dr. K. Cherian-D-F2 Significant shifts of 1332 cm-1 diamond Raman line caused by exciting laser power and particle size Xing-Zhong Zhao, Kuruvilla A. Cherian, Rustum Roy and William B. White, at: The American Ceramic Society Annual Meeting, Indianapolis, USA (1996) New observations on mechanism of growth in combustion flame diamonds K.A. Cherian, J. Litster, V. Rudolph, E.T. White & R. Roy, at: Diamond 1996 - 7th European Conference on Diamond, Diamond-like & Related Materials and 5th International Conference on The New Diamond Science & Technology, Tours, France (September 1996). Diamond needles and tips as engineered growth shapes K.A. Cherian, J. Litster, V. Rudolph & E.T.White, in: Diamond for Electronic Applications, Materials Research Society Symposium (USA) Proceedings vol. 416 (1996) 241-247. A new process for diamond synthesis at low pressures is a potential route to the growth of large single crystal Rustum Roy and Kuruvilla A. Cherian, in: Materials Technology 11 (1996) 6-9. Chemi-mechanical polishing of diamond: new possibilities K.A. Cherian, J. Litster, V. Rudolph, E.T. White & R. Roy, at: 10th International Conference on Surface Modification Technologies, Singapore (September 1996) Two revolutions in diamond synthesis (LPSSS & QQC processes) Kuruvilla A. Cherian and Rustum Roy, Keynote Paper at: PacRim2 - The 2nd International Meeting of Pacific Rim Ceramic Societies, Cairns, Australia, July 1996 Published in CD Rom, 1997 Chemical etching of diamond revisited: past basic research as guide to new processing technologies Kuruvilla A. Cherian, Jim Litster, Victor Rudolph and Edward T. White, in: Chemical Aspects of Electronic Ceramics Processing, Materials Research Society Symposium (USA) Proceedings vol. 495 (1997) 419-424 Oriented diamond growth on platinum via a Me-C-H low pressure processing route Kuruvilla A. Cherian, Scott D. Wolter and Rustum Roy, in: Diamond & Related Materials 6 (1997) 1747-1752 Precipitation of diamond from MexCyHz Solutions at 1 Atm. R. Roy, K.A. Cherian, J.P. Cheng, A. Badzian, C. Langlade, H. Dewan and W. Drawl, in: Materials Research Innovations, 1 (1997) 117-129 Hydrothermal growth of diamond in C-Metal-H2O systems Xing-Zhong Zhao, Rustum Roy, Kuruvilla A. Cherian and A. Badzian. in: Nature, 385 (1997) 513-515 Downshifts of Raman peak in diamond powders Xing-Zhong Zhao, Kuruvilla A. Cherian, Rustum Roy and William B. White, in: Journal of Materials Research, 13 (1998) 1974-1976. Novel approaches in engineering diamond growth and morphology S.R. Rigby, K.A. Cherian, J. Litster, V. Rudolph & E.T. White, at: Chemeca ’98 - 26th Australasian Chemical Engineering Conference, Port Douglas, Australia Liquid phase metastable growth of diamond using non-diamond solid carbon Kuruvilla A. Cherian, Victor Rudolph and Edward T. White, at: Innovations in Materials Conference, Washington D.C., USA (July 1998) Solvo and Hydrothermal approaches to diamond synthesis: the role of metal and hydrogen Rustum Roy and Kuruvilla A. Cherian, at: 3rd International Conference on Solvothermal Reactions, Bordeaux, France (1999) Quantifying CVD diamond growth and morphology: calculating the 'α’ parameter from any two crystal dimensions S.D. Rigby, K.A. Cherian, J.D. Litster, V. Rudolph and E.T. White, in: Diamond & Related Materials 9 (2000) 328-332 Innovations in Materials and Surface Engineering through Simultaneous Multiwavelength and Pulsed Laser Processing Kuruvilla Cherian, Pravin Mistry and Rustum Roy, in: Proceedings of the Ted White Festschrift Symposium, Chemical Engineering Department, University of Queensland, Australia (December 2001) Decrystallization of Diamond under Pulsed Excimer and YAG Lasers and Subsequent Lattice Relaxation A. Badzian, R. Roy, T. Badzian, W. Drawl, P. Mistry, M.C. Turchan, K.A. Cherian, R. Martukanitz, V. Semak and T.M. Petachm, at: International Conference on Metallurgical Coatings and Thin Films, San Diego, USA (April 2002) Decrystallization of diamond by Nd:YAG and excimer lasers and subsequent lattice relaxation A. Badzian, R. Roy, T. Badzian, W. Drawl, P. Mistry, M.C. Turchan, K. Cherian, in: Diamond & Related Materials, 14 (2005) 1562-1570 (Industry sponsored research results have not been published, in accordance with confidentiality agreements) (If interested in similar diamond projects, please contact:
[email protected])
