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Dr Chris Blackman

Materials and Inorganic Chemistry

Dr Chris Blackman
Address: Room 467E, Department of Chemistry, UCL
Phone No: +44 (0)20 7679 4703
Fax No: +44 (0)20 7679 7463
Extension: 24703
Email: c.blackman@ucl.ac.uk
Dr Chris Blackman receiving Provosts Teaching Award

Research areas of interest include:

  • Advanced chemical thin film deposition methods
  • Complex thin film materials synthesis
  • Layered thin film composite materials
  • Inorganic nanostructures 

Summary

My research is centred on the use of Chemical Vapour Deposition (CVD) to deposit thin films of functional materials. 

The applications I have been targeting range from microelectronics to energy (active solar control coatings for energy demand reduction and catalysts for generation of hydrogen from water) through to the environment (gas sensing).

Principally my recent work has focussed on transparent conducting oxides, due to the unusual co-existence of optical transparancy AND electrical conductivity found in these materials, which is combined with chemical reactivity at the surface whilst the materials themselves are also relatively robust.

Recent research on the use of CVD for the deposition of composite thin films composed of bismuth oxide and platinum nanoparticles, which gain the property of being able to split water, evolving hydrogen, under photoillumination, a property not present in either of the constituents of the composite alone, has been featured in a“Young Investigators Award” issue of Inorganic Chimica Acta.

I am also currently interested in the opportunities afforded by CVD to synthesise materials with high purity and precise structural control at the nanometre scale level at the relatively low processing temperatures required for the fabrication of nanocrystalline materials. By altering the deposition conditions to control the chemical reaction it is possible to obtain nanocrystalline powders, nanostructured materials or thin films. Hence CVD is a technique with great promise for synthesis of functional nanomaterials.

Chris Blackman Research Image

Recent research is concerned with the use of AACVD for the synthesis of metal nanoparticle modified metal oxide nanostructures, with the aim of producing highly sensitive and highly selective gas sensors. This work, which is supported by theLeverhulme Trust, has recently been featured in an Emerging Investigators issue of Chemical Communications.

Research Profile

    2013

    • Naik, A. J. T., Warwick, M. E. A., Moniz, S. J. A., Blackman, C. S., Parkin, I. P., Binions, R. (2013). Nanostructured tungsten oxide gas sensors prepared by electric field assisted aerosol assisted chemical vapour deposition. JOURNAL OF MATERIALS CHEMISTRY A 1(5), 1827-1833 doi:10.1039/c2ta01126c. Author URL

    2012

    • Bloor, L. G., Manzi, J., Binions, R., Parkin, I. P., Pugh, D., Afonja, A., Blackman, C. S., Sathasivam, S., Carmalt, C. J. (2012). Tantalum and titanium doped In 2O 3 thin films by aerosol-assisted chemical vapor deposition and their gas sensing properties. Chemistry of Materials 24(15), 2864-2871
    • Cabrera, R. Q., Latimer, E. R., Kafizas, A., Blackman, C. S., Carmalt, C. J., Parkin, I. P. (2012). Photocatalytic activity of needle-like TiO 2/WO 3-x thin films prepared by chemical vapour deposition. Journal of Photochemistry and Photobiology A: Chemistry 239, 60-64
    • Moniz, S. J. A., Bhachu, D., Blackman, C. S., Cross, A. J., Elouali, S., Pugh, D., Quesada Cabrera, R., Vallejos, S. (2012). A novel route to Pt-Bi 2O 3 composite thin films and their application in photo-reduction of water. Inorganica Chimica Acta 380(1), 328-335
    • Navío, C., Vallejos, S., Stoycheva, T., Llobet, E., Correig, X., Snyders, R., Blackman, C., Umek, P., Ke, X., Van Tendeloo, G., Bittencourt, C. (2012). Gold clusters on WO 3 nanoneedles grown via AACVD: XPS and TEM studies. Materials Chemistry and Physics
    • Quesada Cabrera, R., Firth, S., Blackman, C. S., Long, D. -. L., Cronin, L., McMillan, P. F. (2012). Spectroscopic studies of sulfite-based polyoxometalates at high temperature and high pressure. Journal of Solid State Chemistry 186, 171-176
    • Stoycheva, T., Vallejos, S., Blackman, C., Moniz, S. J. A., Calderer, J., Correig, X. (2012). Important considerations for effective gas sensors based on metal oxide nanoneedles films. Sensors and Actuators, B: Chemical 161(1), 406-413
    • Vallejos, S., Stoycheva, T., Llobet, E., Correig, X., Umek, P., Gracia, I., Blackman, C. (2012). Benzene detection on nanostructured tungsten oxide MEMS based gas sensors. Proceedings of the IEEE Conference on Nanotechnology

    2011

    • Thomas, T., Blackman, C. S., Parkin, I. P., Carmalt, C. J. (2011). Titanium arsenide films from the atmospheric pressure chemical vapour deposition of tetrakisdimethylamidotitanium and tert-butylarsine. DALTON T 40(40), 10664-10669 doi:10.1039/c1dt10457h.
    • Vallejos, S., Stoycheva, T., Umek, P., Navio, C., Snyders, R., Bittencourt, C., Llobet, E., Blackman, C., Moniz, S., Correig, X. (2011). Au nanoparticle-functionalised WO3 nanoneedles and their application in high sensitivity gas sensor devices. CHEM COMMUN 47(1), 565-567 doi:10.1039/c0cc02398a.
    • Vallejos, S., Umek, P., Blackman, C. (2011). Aerosol Assisted Chemical Vapour Deposition Control Parameters for Selective Deposition of Tungsten Oxide Nanostructures. JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY. ( Vol. 11 pp.8214-8220). AMER SCIENTIFIC PUBLISHERS.

    2010

    • Moniz, S. J. A., Blackman, C. S., Carmalt, C. J., Hyett, G. (2010). MOCVD of crystalline Bi2O3 thin films using a single-source bismuth alkoxide precursor and their use in photodegradation of water. J MATER CHEM 20(36), 7881-7886 doi:10.1039/c0jm01720e.
    • Potts, S. E., Carmalt, C. J., Blackman, C. S., Abou-Chahine, F., Leick, N., Kessels, W. M. M., Davies, H. O., Heys, P. N. (2010). Bis(cyclopentadienyl) zirconium(IV) amides as possible precursors for low pressure CVD and plasma-enhanced ALD. INORG CHIM ACTA 363(6), 1077-1083 doi:10.1016/j.ica.2009.07.004.
    • Stoycheva, T., Vallejos, S., Calderer, J., Parkin, I., Blackman, C., Correig, X. (2010). Characterization and gas sensing properties of intrinsic and Au-doped WO3 nanostructures deposited by AACVD technique. Procedia Engineering 5, 131-134
    • Thomas, T., Blackman, C. S., Parkin, I. P., Carmalt, C. J. (2010). Atmospheric Pressure Chemical Vapour Deposition of TiCl4 and tBuAsH(2) to Form Titanium Arsenide Thin Films. EUR J INORG CHEM (36), 5629-5634 doi:10.1002/ejic.201000839.

    2009

    • Apostolico, L., Kociok-Kohn, G., Molloy, K. C., Blackman, C. S., Carmalt, C. J., Parkin, I. P. (2009). The reaction of tin(IV) iodide with phosphines: formation of new halotin anions. DALTON T (47), 10486-10494 doi:10.1039/b917722a.
    • Blackman, C. S., Carmalt, C. J., Moniz, S. J. A., Potts, S. E., Davies, H. O., Pugh, D. C. (2009). MOCVD of zirconium oxide from the zirconium guanidinate complex |ZrCp′{2-(iPrN)2CNMe2}2Cl]. ECS Transactions 25(8 PART 1), 561-565
    • Blackman, C. S., Piccirillo, C., Binions, R., Parkin, I. P. (2009). Atmospheric pressure chemical vapour deposition of thermochromic tungsten doped vanadium dioxide thin films for use in architectural glazing. THIN SOLID FILMS 517(16), 4565-4570 doi:10.1016/j.tsf.2008.12.050.
    • Potts, S. E., Carmalt, C. J., Blackman, C. S., Abou-Chahine, F., Pugh, D., Davies, H. O. (2009). Synthesis of Zirconium Guanidinate Complexes and the Formation of Zirconium Carbonitride via Low Pressure CVD. Organometallics 28, 1838- [Submitted]

    2008

    • Ashraf, S., Blackman, C. S., Naisbitt, S. C., Parkin, I. P. (2008). The gas-sensing properties of WO3-x thin films deposited via the atmospheric pressure chemical vapour deposition (APCVD) of WCl6 with ethanol. MEAS SCI TECHNOL 19(2), 025203 doi:10.1088/0957-0233/19/2/025203.
    • Blackman, C. S., Correig, X., Katko, V., Mozalev, A., Parkin, I. P., Alcubilla, R., Trifonov, T. (2008). Templated growth of tungsten oxide micro/nanostructures using aerosol assisted chemical vapour deposition. MATER LETT 62(30), 4582-4584 doi:10.1016/j.matlet.2008.08.027.
    • Parkin, I. P., Binions, R., Piccirillo, C., Blackman, C. S., Manning, T. D. (2008). Thermochrornic Coatings for Intelligent Architectural Glazing. J NANO RES-SW 2, 1-20
    • Potts, S. E., Carmalt, C. J., Blackman, C. S., Leese, T., Davies, H. O. (2008). Tungsten imido complexes as precursors to tungsten carbonitride thin films. Dalton Transactions , 5730-5736 doi:10.1039/b808650h.

    2007

    • Ashraf, S., Binions, R., Blackman, C. S., Parkin, I. P. (2007). The APCVD of tungsten oxide thin films from reaction of WCl6 with ethanol and results on their gas-sensing properties. POLYHEDRON 26(7), 1493-1498 doi:10.1016/j.poly.2006.11.017.
    • Ashraf, S., Blackman, C. S., Palgrave, R. G., Naisbitt, S. C., Parkin, I. P. (2007). Aerosol assisted chemical vapour deposition of WO3 thin films from tungsten hexacarbonyl and their gas sensing properties. J MATER CHEM 17(35), 3708-3713 doi:10.1039/b705166b.
    • Ashraf, S., Blackman, C. S., Palgrave, R. G., Parkin, I. P. (2007). Aerosol-assisted chemical vapour deposition of WO3 thin films using polyoxometallate precursors and their gas sensing properties. Journal of Materials Chemistry 17, 1063-1070 doi:10.1039/b617982g.
    • Boscher, N. D., Blackman, C. S., Carmalt, C. J., Parkin, I. P., Prieto, A. G. (2007). Atmospheric pressure chemical vapour deposition of vanadium diselenide thin films. Applied Surface Science 253(14), 6041-6046 doi:10.1016/j.apsusc.2007.01.002.
    • Hyett, G., Blackman, C. S., Parkin, I. P. (2007). The effect of oxygen-containing reagents on the crystal morphology and orientation in tungsten oxide thin films deposited via atmospheric pressure chemical vapour deposition (APCVD) on glass substrates. FARADAY DISCUSS 136, 329-343 doi:10.1039/b615877c.
    • Qureshi, U., Blackman, C., Hyett, G., Parkin, I. P. (2007). Tungsten oxide and tungsten oxide-titania thin films prepared by aerosol-assisted deposition - Use of preformed solid nanoparticles. EUR J INORG CHEM (10), 1415-1421 doi:10.1002/ejic.200601211.

    2006

    • Ashraf, S., Blackman, C., S, H., G, P., I, P. (2006). Aerosol assisted chemical vapour deposition of MoO3 and MoO2 thin films on glass from molybdenum polyoxometallate precursors; thermophoresis and gas phase nanoparticle formation. Journal of Materials Chemistry 16, 3575-3582 doi:10.1039/b607335b.
    • Iwaki, T., Covington, J. A., Gardner, J. W., Udrea, F., Blackman, C. S., Parkin, I. P. (2006). SOI-CMOS based single crystal silicon microheaters for gas sensors. Proceedings of IEEE Sensors , 460-463
    • Qureshi, U., Manning, T. D., Blackman, C., Parkin, I. P. (2006). Composite thermochromic thin films: (TiO2)-(VO2) prepared from titanium isopropoxide,VOCl3 and water. POLYHEDRON 25(2), 334-338 doi:10.1016/j.poly.2005.08.018.

    2005

    • Blackman, C. S., Parkin, I. P. (2005). Atmospheric pressure chemical vapor deposition of crystalline monoclinic WO3 and WO3-x thin films from reaction of WCl6 with O-containing solvents and their photochromic and electrochromic properties. Chemistry of Materials 17, 1583-1590 doi:10.1021/cm0403816.
    • Manning, T. D., Parkin, I. P., Blackman, C., Qureshi, U. (2005). APCVD of thermochromic vanadium dioxide thin films - solid solutions V2-xMxO2 (M = Mo, Nb) or composites VO2 : SnO2. J MATER CHEM 15(42), 4560-4566 doi:10.1039/b510552h.

    2004

    • Apostolico, L., Mahon, M. F., Molloy, K. C., Binions, R., Blackman, C. S., Carmalt, C. J., Parkin, I. P. (2004). The reaction of GeCl4 with primary and secondary phosphines. Dalton Transactions (3), 470-475 doi:10.1039/b315378a.
    • Blackman, C. S., Carmalt, C. J., Manning, T. D., Parkin, I. P., Apostolico, L., Molloy, K. C. (2004). Low temperature deposition of crystalline chromium phosphide films using dual-source atmospheric pressure chemical vapour deposition. Applied Surface Science 233, 24-28
    • Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Apostolico, L., Molloy, K. C. (2004). Atmospheric-pressure chemical vapor deposition of group IVb metal phosphide thin films from tetrakisdimethylamidometal complexes and cyclohexylphosphine. Chemistry of Materials 16, 1120-1125 doi:10.1021/cm031161f.
    • Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Molloy, K. C., Apostolico, L. (2004). Atmospheric-pressure CVD of vanadium phosphide thin films from reaction of tetrakisdimethylamidovanadium and cyclohexylphosphine. CHEM VAP DEPOSITION 10(5), 253-255

    2003

    • Blackman, C. S., Carmalt, C. J., Manning, T. D., O'Neill, S. A., Parkin, I. P., Apostolico, L., Molloy, K. C. (2003). Dual-source atmospheric pressure CVD of amorphous molybdenum phosphide films on glass using molybdenum(v) chloride and cyclohexylphosphine. Chemical Vapor Deposition 9(1), 10-13
    • Blackman, C. S., Carmalt, C. J., Manning, T. D., O'Neill, S. A., Parkin, I. P., Apostolico, L., Molloy, K. C. (2003). Dual-source atmospheric pressure CVD of amorphous molybdenum phosphide films on glass using molybdenum(v) chloride and cyclohexylphosphine. Chemical Vapor Deposition 9(1), 10-13
    • Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Apostolico, L., Molloy, K. C. (2003). Dual-source chemical vapour deposition of titanium(III) phosphide from titanium tetrachloride and tristrimethylsilylphosphine. Applied Surface Science 211, 2-5
    • Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Molloy, K. C., Apostolico, L. (2003). Chemical vapour deposition of group Vb metal phosphide thin films. Journal of Materials Chemistry 13, 1930-1935 doi:10.1039/b304084b.
    • Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Molloy, K. C., Apostolico, L. (2003). Titanium Phosphide Coatings From the Atmospheric Pressure CVD Reaction of TiCl4 with PRxH3-x (R = Cyhex; or R = SiMe3 where x-3). Chemical Vapour Deposition XVI and EuroCVD 14. ( Vol. 2 pp.1387-1394). Pennington, New Jersey: The Electrochemical Society, Inc..
    • Blackman, C. S., Carmalt, C. J., Parkin, I. P., O'Neill, S. A., Molloy, K. C., Apostolico, L. (2003). Chemical vapour deposition of crystalline thin films of tantalum phosphide. Materials Letters 57, 2634-2636

    2002

    • Binions, R., Blackman, C. S., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Molloy, K., Apostilco, L. (2002). Tin phosphide coatings from the atmospheric pressure chemical vapour deposition of SnX4 (X = Cl or Br) and PRxH3-x (R = Cyc(hex) or phenyl). Polyhedron 21(19), 1943-1947 doi:10.1016/S0277-5387(02)01081-1.
    • Blackman, C. S., Carmalt, C. J., Parkin, I. P., Apostolico, L., Molloy, K. C., White, A. J. P., Williams, D. J. (2002). Single-source CVD routes to titanium phosphide. Journal of the Chemical Society, Dalton Transactions (13), 2702-2709
    • Blackman, C., Carmalt, C. J., Parkin, I. P., O'Neill, S., Apostolico, L., Molloy, K. C., Rushworth, S. (2002). Titanium phosphide coatings from the atmospheric pressure chemical vapor deposition of TiCl4 and RPH2 (R = t-Bu, Ph, Cy-Hex). Chemistry of Materials 14(7), 3167-3173

    2001

    • Blackman, C., Carmalt, C. J., O'Neill, S. A., Parkin, I. P., Apostilco, L., Molloy, K. C. (2001). Dual source atmospheric pressure chemical vapour deposition of TiP films on glass using TiCl4 and PH2But. Journal of Materials Chemistry 11(10), 2408-2409

Research Overview

My research is centred on the use of Chemical Vapour Deposition (CVD) to deposit thin films of functional materials. 

This has included the use of atmospheric variants to deposit thin films of various metal phosphides, oxides and selenides, the use of aerosol assisted CVD for the deposition of various nanostructured oxide materials and also the  use of low pressure techniques for deposition of thin films of zirconium and tungsten carbonitrides. 

The applications I have been targeting range from microelectronics to energy (active solar control coatings for energy demand reduction and catalysts for generation of hydrogen from water) through to the environment (gas sensing).

Principally my recent work has focussed on transparent conducting oxides, due to the unusual co-existence of optical transparancy AND electrical conductivity found in these materials, which is combined with chemical reactivity at the surface whilst the materials themselves are also relatively robust.

For instance my group has recently demonstrated the use of LPCVD for phase selective deposition of thin films of bismuth oxide, which have been shown to be active photocatalysts in the oxidation of water.

bismuth oxide
Schematic

Recent research on the use of CVD for the deposition of composite thin films composed of bismuth oxide and platinum nanoparticles, which gain the property of being able to split water, evolving hydrogen, under photoillumination, a property not present in either of the constituents of the composite alone, has been featured in a“Young Investigators Award” issue of Inorganic Chimica Acta.


Methods of nanoparticle synthesis must be developed in accordance with green chemistry, but these techniques must also be compatible with device manufacture to ensure that green principles are followed throughout the fabrication process and also to ensure the potential benefits of the materials are realised. New manufacturing strategies that are additive rather than subtractive, i.e. bottom-up synthesis strategies, can reduce energy requirements and waste generation. A potentially greener approach to top-down or wet-chemical methods of nanoparticle synthesis is to employ direct deposition from the vapour phase, which provides increased atom efficiency and reduced waste production.

Chris Blackman Research Image

I am currently interested in the opportunities afforded by AACVD to synthesise materials with high purity and precise structural control at the nanometre scale level at the relatively low processing temperatures required for the fabrication of nanocrystalline materials. By altering the deposition conditions to control the chemical reaction it is possible to obtain nanocrystalline powders, nanostructured materials or thin films. Hence AACVD is a technique with great promise for synthesis of functional nanomaterials.

Recent research is concerned with the use of AACVD for the synthesis of metal nanoparticle modified metal oxide nanostructures, with the aim of producing highly sensitive and highly selective gas sensors. This work, which is supported by the Leverhulme Trust, has recently been featured in an Emerging Investigators issue of Chemical Communications.

Teaching Overview

I also actively carry out research in teaching in higher education, specifically my interests are in the use of web-based resources for enhancing learning outcomes from traditional methods of teaching at university level. This work has been supported by a variety of grants including, most recently, funding from UCL:

Enhancing the Chemistry programme using Virtual Learning Environments (VLE)

UCL Futures Grant

Developing web-based prelab tutorial support for teaching in the chemistry laboratory

UCL E-learning Development Grant 

This work has recently been acknowledged via a prestigious Provosts Teaching Award at UCL.

All Publications

Selected Publications

  1. S. Vallejos, T. Stoycheva, P. Umek, C. Navio, R. Snyders, C. Bittencourt, E. Llobet, C. Blackman, S. Moniz, X. Correig

    Au-nanoparticle functionalised WO3 nanoneedles and their application in high sensitivity gas sensor devices
    Chem. Commun., 2011, 47, 565
    This article was an invited contribution to a special 'Emerging Investigators' issue of Chemical Communications and this article is currently available free of charge.
    A new method of synthesising nanoparticle-functionalised nanostructured materials via Aerosol Assisted Chemical Vapour Deposition (AACVD) has been developed. Co-deposition of Au nanoparticles with WO3 nanoneedles has been used to deposit a sensing layer directly onto gas sensor substrates providing devices with a six-fold increase in response to low concentrations of a test analyte (ethanol).

  2. S.J.A. Moniz, C.S. Blackman, C.J. Carmalt, G. Hyett

    MOCVD of crystalline Bi2O3 thin films using a single-source bismuth alkoxide precursor and their use in photodegradation of water
    J. Mater. Chem., 2010, 20, 7881
    Bismuth(III) tert-butoxide [Bi(OtBu)3] was utilised as a single-source precursor to controllably deposit thin films of different phases of bismuth oxide (Bi2O3) on glass substrates via low-pressure chemical vapour deposition (LPCVD). Band gaps for the different phases have been measured (Eg = 2.3–3.0 eV) and the films displayed excellent photodegradation of water under near-UV irradiation.

  3. S. Ashraf, C.S. Blackman, S. Naisbitt, R.G. Palgrave, I.P. Parkin

    Aerosol assisted chemical vapour deposition of WO3 thin films from tungsten hexacarbonyl and their gas sensing properties
    J. Mater. Chem., 2007, 17, 3708
    Aerosol assisted chemical vapour deposition (AACVD) reactions of tungsten hexacarbonyl, [W(CO)6], in acetone, methanol, acetonitrile and a 50 : 50 mixture of acetone and toluene resulted in the deposition of blue partially reduced WO3−x films which showed preferred orientation along the (0 1 0) direction. The WO3 films functioned as gas sensitive resistors for the detection of NO2. Responses were recorded at minimum concentrations of 1.03 ppm of NO2, significantly exceeding those of commercial screen printed sensors.

  4. S. Ashraf, C.S. Blackman, I.P. Parkin

    Aerosol assisted chemical vapour deposition of tungsten oxide thin films on glass from polyoxometallate precursors and their gas-sensing properties
    J. Mater. Chem., 2007, 17, 1063
    Aerosol-assisted chemical vapour deposition (AACVD) of polytungstates in acetonitrile or water yielded thin films of tungsten oxide on glass. The WO3 films functioned as gas sensors showing a linear change in electrical resistance upon exposure to trace amounts of ethanol and nitrogen dioxide vapour in air, with responses comparable to that of screen-printed sensors and a faster speed of response.