Frontiers of Chemical Science and Engineering

, Volume 10, Issue 4, pp 441–458 | Cite as

Where physics meets chemistry: Thin film deposition from reactive plasmas

Review Article

Abstract

Functionalising surfaces using polymeric thin films is an industrially important field. One technique for achieving nanoscale, controlled surface functionalization is plasma deposition. Plasma deposition has advantages over other surface engineering processes, including that it is solvent free, substrate and geometry independent, and the surface properties of the film can be designed by judicious choice of precursor and plasma conditions. Despite the utility of this method, the mechanisms of plasma polymer growth are generally unknown, and are usually described by chemical (i.e., radical) pathways. In this review, we aim to show that plasma physics drives the chemistry of the plasma phase, and surface-plasma interactions. For example, we show that ionic species can react in the plasma to form larger ions, and also arrive at surfaces with energies greater than 1000 kJ∙mol–1 (>10 eV) and thus facilitate surface reactions that have not been taken into account previously. Thus, improving thin film deposition processes requires an understanding of both physical and chemical processes in plasma.

Keywords

thin films plasma physics plasma chemistry functionalization polymer 

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References

  1. 1.
    Chatelier R C, Dai L, Griesser H J, Li S, Zientek P, Lohmann D, Chabrecek P U S. Patent, 6623747, 2003-09-23Google Scholar
  2. 2.
    Moustafa M, Simpson C, Glover M, Dawson R A, Tesfaye S, Creagh F M, Haddow D, Short R, Heller S, MacNeil S. A new autologous keratinocyte dressing treatment for non-healing diabetic neuropathic foot ulcers. Diabetic Medicine, 2004, 21(7): 786–789CrossRefGoogle Scholar
  3. 3.
    Yasuda H. Plasma Polymerization. New York: Academic Press, 1985Google Scholar
  4. 4.
    Kettle A, Beck A J, O’Toole L, Jones F, Short R. Plasma polymerisation for molecular engineering of carbon-fibre surfaces for optimised composites. Composites Science and Technology, 1997, 57(8): 1023–1032CrossRefGoogle Scholar
  5. 5.
    Lopattananon N, Kettle A, Tripathi D, Beck A J, Duval E, France R M, Short R D, Jones F R. Interface molecular engineering of carbonfibercomposites. Composites. Part A, Applied Science and Manufacturing, 1999, 30(1): 49–57CrossRefGoogle Scholar
  6. 6.
    Beck A J, Jones F R, Short R D. Plasma copolymerization as a route to the fabrication of new surfaces with controlled amounts of specific chemical functionality. Polymer, 1996, 37(24): 5537–5539CrossRefGoogle Scholar
  7. 7.
    Michelmore A, Whittle J D, Short R D, Boswell RW, Charles C. An Experimental and analytical study of an asymmetric capacitively coupled plasma used for plasma polymerization. Plasma Processes and Polymers, 2014, 11(9): 833–841CrossRefGoogle Scholar
  8. 8.
    Suzuki K, Nakamura K, Ohkubo H, Sugai H. Power transfer efficiency and mode jump in an inductive RF discharge. Plasma Sources Science & Technology, 1998, 7(1): 13–20CrossRefGoogle Scholar
  9. 9.
    Ward R J. Molecular engineering of surfaces by plasma copolymerization and enhanced cell attachment and spreading. Dissertation for the Doctoral Degree. UK: University of Durham, 1989Google Scholar
  10. 10.
    Beyer D, Knoll W, Ringsdorf H, Wang J H, Timmons R B, Sluka P. Reduced protein adsorption on plastics via direct plasma deposition of triethylene glycol monoallyl ether. Journal of Biomedical Materials Research. Part A, 1997, 36(2): 181–189CrossRefGoogle Scholar
  11. 11.
    Padron-Wells G, Estrada-Raygoza I C, Thamban P L S, Nelson C T, Chung C W, Overzet L J, Goeckner M J. Understanding the synthesis of ethylene glycol pulsed plasma discharges. Plasma Processes and Polymers, 2013, 10(2): 119–135CrossRefGoogle Scholar
  12. 12.
    Chen R T, Muir B W, Thomsen L, Tadich A, Cowie B C C, Such G K, Postma A, McLean K M, Caruso F. New insights into the substrate plasma polymer interface. Journal of Physical Chemistry B, 2011, 115(20): 6495–6502CrossRefGoogle Scholar
  13. 13.
    Daw R, O’Leary T, Kelly J, Short R D, Cambray-Deakin M, Devlin A J, Brook I M, Scutt A, Kothari S. Molecular engineering of surfaces by plasma copolymerization and enhanced cell attachment and spreading. Plasmas and Polymers, 1999, 4(2-3): 113–132CrossRefGoogle Scholar
  14. 14.
    Daw R, Candan S, Beck A, Devlin A, Brook I, MacNeil S, Dawson D A, Short R D. Plasma copolymer surfaces of acrylic acid/1, 7-octadiene: Surface characterisation and the attachment of ROS 17/2. 8-osteoblast-like cells. Biomaterials, 1998, 19(19): 1717–1725Google Scholar
  15. 15.
    Michelmore A, Steele D A, Robinson D E, Whittle J D, Short R D. The link between mechanisms of deposition and the physicochemical properties of plasma polymer films. Soft Matter, 2013, 9(26): 6167–6175CrossRefGoogle Scholar
  16. 16.
    Whittle J D, Short R D, Douglas C, Davies J. Differences in the aging of allyl alcohol, acrylic acid, allylamine, and octa-1, 7-diene plasma polymers as studied by X-ray photoelectron spectroscopy. Chemistry of Materials, 2000, 12(9): 2664–2671CrossRefGoogle Scholar
  17. 17.
    Gengenbach T R, Chatelier R C, Griesser H J. Characterization of the ageing of plasma-deposited polymer films: Global analysis of xray photoelectron spectroscopy data. Surface and Interface Analysis, 1996, 24(4): 271–281CrossRefGoogle Scholar
  18. 18.
    Haddow D B, Steele D, Short R D, Dawson R A, Macneil S. Plasma–polymerized surfaces for culture of human keratinocytes and transfer of cells to an in vitro wound–bed model. Journal of Biomedical Materials Research. Part A, 2003, 64A(1): 80–87CrossRefGoogle Scholar
  19. 19.
    Padron-Wells G, Jarvis B C, Jindal A K, Goeckner M J. Understanding the synthesis of DEGVE pulsed plasmas for application to ultra thin biocompatible interfaces. Colloids and Surfaces. B, Biointerfaces, 2009, 68(2): 163–170CrossRefGoogle Scholar
  20. 20.
    Michelmore A, Bryant P M, Steele D A, Vasilev K, Bradley J W, Short R D. Role of positive ions in determining the deposition rate and film chemistry of continuous wave hexamethyldisiloxane plasmas. Langmuir, 2011, 27(19): 11943–11950CrossRefGoogle Scholar
  21. 21.
    Michelmore A, Gross-Kosche P, Al-Bataineh S A, Whittle J D, Short R D. On the effect of monomer chemistry on growth mechanisms of nonfouling PEG-like plasma polymers. Langmuir, 2013, 29(8): 2595–2601CrossRefGoogle Scholar
  22. 22.
    Choukourov A, Biederman H, Slavinska D, Hanley L, Grinevich A, Boldryeva H, Mackova A. Mechanistic studies of plasma polymerization of allylamine. Journal of Physical Chemistry B, 2005, 109(48): 23086–23091CrossRefGoogle Scholar
  23. 23.
    Michelmore A, Charles C, Boswell R W, Short R D, Whittle J D. Defining plasma polymerization: New insight into what we should be measuring. ACS Applied Materials & Interfaces, 2013, 5(12): 5387–5391CrossRefGoogle Scholar
  24. 24.
    Daunton C, Smith L E, Whittle J D, Short R D, Steele D A, Michelmore A. Plasma parameter aspects in the fabrication of stable amine functionalized plasma polymer films. Plasma Processes and Polymers, 2015, 12(8): 817–826CrossRefGoogle Scholar
  25. 25.
    Saboohi S, Jasieniak M, Coad B R, Griesser H J, Short R D, Michelmore A. Comparison of plasma polymerization under collisional and collision-less pressure regimes. Journal of Physical Chemistry B, 2015, 119(49): 15359–15369CrossRefGoogle Scholar
  26. 26.
    Zhang Z H, Liu S L, Shi Y, Dou J, Fang S M. DNA detection and cell adhesion on plasma-polymerized pyrrole. Biopolymers, 2014, 101(5): 496–503CrossRefGoogle Scholar
  27. 27.
    Wang L, Liu X J, Hao J, Chu L Q. Long-range surface plasmon resonance sensors fabricated with plasma polymerized fluorocarbon thin films. Sensors and Actuators. B, Chemical, 2015, 215: 368–372CrossRefGoogle Scholar
  28. 28.
    Jiang Z, Jiang Z J. Plasma techniques for the fabrication of polymer electrolyte membranes for fuel cells. Journal of Membrane Science, 2014, 456: 85–106CrossRefGoogle Scholar
  29. 29.
    Hua J, Zhanga C, Jiangb L, Fanga S, Zhanga X, Wanga X, Menga Y. Plasma graft-polymerization for synthesis of highly stable hydroxide exchange membrane. Journal of Power Sources, 2014, 248: 831–838CrossRefGoogle Scholar
  30. 30.
    Zhao X Y, Wang MZ, Ji J Q, Wang T H, Yang F, Du J M. Structural analysis and dielectric property of novel conjugated polycyanurates. Polymer Engineering and Science, 2014, 54(4): 812–817CrossRefGoogle Scholar
  31. 31.
    Li P H, Li L M, Wang W H, Jin W H, Liu X M, Yeung K W K, Chu P K. Enhanced corrosion resistance and hemocompatibility of biomedical NiTi alloy by atmospheric-pressure plasma polymerized fluorine-rich coating. Applied Surface Science, 2014, 297: 109–115CrossRefGoogle Scholar
  32. 32.
    Feng Y E, Liao X P, Wang Y N, Shi B. Improvement in leather surface hydrophobicity through low-pressure cold plasma polymerization. Journal of the American Leather Chemistry Association, 2014, 109(3): 89–95Google Scholar
  33. 33.
    Yang Z L, Xiong K Q, Qi P K, Yang Y, Tu Q F, Wang J, Huang N. Gallic acid tailoring surface functionalities of plasma-polymerized allylamine-coated 316L SS to selectively direct vascular endothelial and smooth muscle cell fate for enhanced endothelialization. ACS Applied Materials & Interfaces, 2014, 6(4): 2647–2656CrossRefGoogle Scholar
  34. 34.
    Li J W, Wu Z X, Huang C J, Liu H M, Huang R J, Li L F. Mechanical properties of cyanate ester/epoxy nanocomposites modified with plasma functionalized MWCNTs. Composites Science and Technology, 2014, 90: 166–173CrossRefGoogle Scholar
  35. 35.
    Sun Y Y, Liang Q, Chi H J, Zhang Y J, Shi Y, Fang D N, Li F X. The Application of gas plasma technologies in surface modification of aramid fiber. Fibers and Polymers, 2014, 15(1): 1–7CrossRefGoogle Scholar
  36. 36.
    Tian M, Yin Y, Yang C, Zhao B, Song J, Liu J, Li X M, He T. CF4 plasma modified highly interconnective porous polysulfone membranes for direct contact membrane distillation (DCMD). Desalination, 2015, 369: 105–114CrossRefGoogle Scholar
  37. 37.
    Ma G Q, Liu Y, Wei S, Sheng J. Surface modification of polypropylene by ethylene plasma and its induced ß-form in polypropylene. Chinese Journal of Polymer Science, 2015, 33(5): 669–673CrossRefGoogle Scholar
  38. 38.
    Wan S J, Wang L, Xu X J, Zhao C H, Liu X D. Controllable surface morphology and properties via mist polymerization on a plasmatreated polymethyl methacrylate surface. Soft Matter, 2014, 10(6): 903–910CrossRefGoogle Scholar
  39. 39.
    Zhang Z G, Zhang T Z, Li J S, Ji Z L, Zhou H M, Zhou X F, Gu N. Preparation of poly(L-lactic acid)-modified polypropylene mesh and its antiadhesion in experimental abdominal wall defect repair. Journal of Biomedical Materials Research Part B, 2014, 102(1): 12–21CrossRefGoogle Scholar
  40. 40.
    Denaro A R, Owens P A, Crawshaw A. Glow discharge polymerization—styrene. European Polymer Journal, 1968, 4(1): 93–106CrossRefGoogle Scholar
  41. 41.
    Westwood A R. Glow discharge polymerization—rates and mechanisms of polymer formation. European Polymer Journal, 1971, 7(4): 363–375CrossRefGoogle Scholar
  42. 42.
    Michelmore A, Steele D A, Whittle J D, Bradley J W, Short R D. Nanoscale deposition of chemically functionalised films via plasma polymerisation. RSC Advances, 2013, 3(33): 13540–13557CrossRefGoogle Scholar
  43. 43.
    Chabert P, Braithwaite N. Physics of Radio-Frequency Plasmas. Cambridge: Academic Press, 2011CrossRefGoogle Scholar
  44. 44.
    Lieberman M A, Lichtenberg A J. Principles of Plasma Discharges and Materials Processing. Chichester: John Wiley and Sons, 1994Google Scholar
  45. 45.
    Hulburt E O. Atmospheric ionization by cosmic radiation. Physical Review, 1931, 37(1): 1–8CrossRefGoogle Scholar
  46. 46.
    Blanksby S J, Ellison G B. Bond dissociation energies of organic molecules. Accounts of Chemical Research, 2003, 36(4): 255–263CrossRefGoogle Scholar
  47. 47.
    Johnston E E, Beyers J D, Ratner B D. Plasma deposition and surface characterization of oligoglyme, dioxane, and crown ether nonfouling films. Langmuir, 2005, 21(3): 870–881CrossRefGoogle Scholar
  48. 48.
    Menzies D J, Cowie B, Fong C, Forsythe J S, Gengenbach T R, McLean K M, Puskar L, Textor M, Thomsen L, Tobin M, Muir B W. One-step method for generating PEG-Like plasma polymer gradients: Chemical characterization and analysis of protein interactions. Langmuir, 2010, 26(17): 13987–13994CrossRefGoogle Scholar
  49. 49.
    Flory P J. Principles of Polymer Chemistry. New York: Cornell University Press, 1953Google Scholar
  50. 50.
    Agarwal S, Quax G W W, van de Senden M C M, Maroudas D, Aydil E S. Measurement of absolute radical densities in a plasma using modulated-beam line-of-sight threshold ionization mass spectrometry. Journal of Vacuum Science and Technology Part A, 2004, 22(1): 71–81CrossRefGoogle Scholar
  51. 51.
    Booth J P, Corr C S, Curley G A, Jolly J, Guillon J, Földes T. Fluorine negative ion density measurement in a dual frequency capacitive plasma etch reactor by cavity ring-down spectroscopy. Applied Physics Letters, 2006, 88(15): 151502CrossRefGoogle Scholar
  52. 52.
    Whittle J D, Short R D, Steele D A, Bradley J W, Bryant P M, Jan F, Biederman H, Serov A A, Choukurov A, Hook A L, Ciridon WA, Ceccone G, Hegemann D, Korner E, Michelmore A. Variability in plasma polymerization processes—an international round-robin study. Plasma Processes and Polymers, 2013, 10(9): 767–778CrossRefGoogle Scholar
  53. 53.
    Williams T, Hayes M W. Polymerization in a glow discharge. Nature, 1966, 209(5025): 769–773CrossRefGoogle Scholar
  54. 54.
    Chapman B. Glow Discharge Processes. Chichester: John Wiley and Sons, 1980Google Scholar
  55. 55.
    Doyle J R. Chemical kinetics in low pressure acetylene radio frequency glow discharges. Journal of Applied Physics, 1997, 82(10): 4763–4771CrossRefGoogle Scholar
  56. 56.
    O’Toole L, Mayhew C A, Short R D. On the plasma polymerisation of allyl alcohol: An investigation of ion-molecule reactions using a selected ion flow tube. Journal of the Chemical Society, Faraday Transactions, 1997, 93(10): 1961–1964CrossRefGoogle Scholar
  57. 57.
    Stoykov S, Eggs C, Kortshagen U. Plasma chemistry and growth of nanosized particles in a C2H2 RF discharge. Journal of Physics. D, Applied Physics, 2001, 34(14): 2160–2173CrossRefGoogle Scholar
  58. 58.
    Oh J S, Bradley J W. Heavy ion formation in plasma jet polymerization of heptylamine at atmospheric pressure. Plasma Processes and Polymers, 2013, 10(10): 839–842Google Scholar
  59. 59.
    O’Toole L, Short R D, Ameen A P, Jones F R. Mass spectrometry of and deposition-rate measurements from radiofrequency-induced plasmas of methyl isobutyrate, methyl methacrylate and n-butyl methacrylate. Journal of the Chemical Society, Faraday Transactions, 1995, 91(9): 1363–1370CrossRefGoogle Scholar
  60. 60.
    Bohm D. Minimum ionic kinetic energy for a stable sheath. In: Guthrie A, Wakerling R K, eds. The Characteristics of Electrical Discharges in Magnetic Fields. London: McGrawHill, 1949, 77–86Google Scholar
  61. 61.
    Vender D, Boswell R W. Numerical modeling of low-pressure RF plasma. IEEE Transactions on Plasma Science, 1990, 18(4): 725–732CrossRefGoogle Scholar
  62. 62.
    Jacobs D C. Reactive collisions of hyperthermal energy molecular ions with solid surfaces. Annual Review of Physical Chemistry, 2002, 53(1): 379–407CrossRefGoogle Scholar
  63. 63.
    Titus M J, Nest D, Graves D B. Absolute vacuum ultraviolet flux in inductively coupled plasmas and chemical modifications of 193 nm photoresist. Applied Physics Letters, 2009, 94(17): 171501CrossRefGoogle Scholar
  64. 64.
    Truica-Marasescu F, Wertheimer M R. Vacuum-ultraviolet photopolymerisation of amine-rich thin films. Macromolecular Chemistry and Physics, 2008, 209(10): 1043–1049CrossRefGoogle Scholar
  65. 65.
    Barton D, Bradley J W, Gibson K J, Steele D A, Short R D. An in situ comparison between VUV photon and ion energy fluxes to polymer surfaces immersed in an RF plasma. Journal of Physical Chemistry B, 2000, 104(30): 7150–7153CrossRefGoogle Scholar
  66. 66.
    Haller I, White P. Polymerization of butadiene gas on surfaces under low energy electron bombardment. Journal of Physical Chemistry, 1963, 67(9): 1784–1788CrossRefGoogle Scholar
  67. 67.
    Peter S, Graupner K, Grambole D, Richter F. Comparative experimental analysis of the a-C:H deposition processes using CH4 and C2H2 as precursors. Journal of Applied Physics, 2007, 102 (5): 053304CrossRefGoogle Scholar
  68. 68.
    Shen M, Bell A T. A review of recent advances in plasma polymerization. In: Plasma Polymerization. ACS Symposium Series. Washington, DC: American Chemical Society, 1979, 1–33CrossRefGoogle Scholar
  69. 69.
    Friedrich J. Plasma processes and polymers, mechanisms of plasma polymerization—reviewed from a chemical point of view. Plasma Processes and Polymers, 2011, 8(9): 783–802CrossRefGoogle Scholar
  70. 70.
    Milella A, Palumbo F, Favia P, Cicala G, d’Agostino R. Continuous and modulated deposition of fluorocarbon films from c-C4F8 plasmas. Plasma Processes and Polymers, 2004, 1(2): 164–170CrossRefGoogle Scholar
  71. 71.
    Hegemann D, Hanselmann B, Blanchard N, Amberg M. Plasmasubstrate interaction during plasma deposition on polymers. Contributions to Plasma Physics, 2014, 54(2): 162–169CrossRefGoogle Scholar
  72. 72.
    Thiry D, Konstantinidis S, Cornil J, Snyders R. Plasma diagnostics for the low-pressure plasma polymerization process: A critical review. Thin Solid Films, 2016, 606: 19–44CrossRefGoogle Scholar
  73. 73.
    Ershov S, Khelifa F, Lemaur V, Cornil J, Cossement D, Habibi Y, Dubois P, Snyders R. Free radical generation and concentration in a plasma polymer: The effect of aromaticity. ACS Applied Materials & Interfaces, 2014, 6(15): 12395–12405CrossRefGoogle Scholar
  74. 74.
    Von Keudell A, Schwartz-Selinger T, Meier M, Jacob W. Direct identification of the synergism between methyl radicals and atomic hydrogen during growth of amorphous hydrogenated carbon films. Applied Physics Letters, 2000, 76(6): 676–678CrossRefGoogle Scholar
  75. 75.
    McNaught A D, Wilkinson A. IUPAC Compendium of Chemical Terminology, 2nd ed. Oxford: Blackwell Scientific Publications, 1997Google Scholar
  76. 76.
    O’Toole L, Beck A J, Ameen A P, Jones F R, Short R D. Radiofrequency-induced plasma polymerisation of propenoic acid and propanoic acid. Journal of the Chemical Society, Faraday Transactions, 1995, 91(21): 3907–3912CrossRefGoogle Scholar
  77. 77.
    Brookes P N, Fraser S, Short R D, Hanley L, Fuoco E, Roberts A, Hutton S J. The effect of ion energy on the chemistry of air-aged polymer films grown from the hyperthermal polyatomic ion Si2OMe+ 5. Electron Spectroscopy and Related Phenomena, 2001, 121(1-3): 281–297CrossRefGoogle Scholar
  78. 78.
    Beck A J, Candan S, Short R D, Goodyear A, Braithwaite N, St J. The role of ions in the plasma polymerization of allylamine. Journal of Physical Chemistry B, 2001, 105(24): 5730–5736CrossRefGoogle Scholar
  79. 79.
    Michelmore A, Whittle J D, Short R D. The importance of ions in low pressure PECVD plasmas. Frontiers in Physics, 2015, 3: 3CrossRefGoogle Scholar
  80. 80.
    von Keudell A. Surface processes during thin-film growth. Plasma Sources Science & Technology, 2000, 9(4): 455–467CrossRefGoogle Scholar
  81. 81.
    Khelifa F, Ershov S, Habibi Y, Snyders R, Dubois P. Free-radicalinduced grafting from plasma polymer surfaces. Chemical Reviews, 2016, 116(6): 3975–4005CrossRefGoogle Scholar
  82. 82.
    Coad B R, Styan K E, Meagher L. One step ATRP initiator immobilization on surfaces leading to gradient-grafted polymer brushes. ACS Applied Materials & Interfaces, 2014, 6(10): 7782–7789CrossRefGoogle Scholar
  83. 83.
    Blanchard N E, Hanselmann B, Drosten J, Heunberger M, Hegemann D. Densification and hydration of HMDSO plasma polymers. Plasma Processes and Polymers, 2015, 12(1): 32–41CrossRefGoogle Scholar
  84. 84.
    Ryssy J, Prioste-Amaral E, Assuncao D F N, Rogers N, Kirby G T S, Smith L E, Michelmore A. Chemical and physical processes in the retention of functional groups in plasma polymers studied by plasma phase mass spectroscopy. Physical Chemistry Chemical Physics, 2016, 18(6): 4496–4504CrossRefGoogle Scholar
  85. 85.
    Hopp I, Michelmore A, Smith L E, Robinson D E, Bachhuka A, Mierczynska A, Vasilev K. The influence of substrate stiffness gradients on primary human dermal fibroblasts. Biomaterials, 2013, 34(21): 5070–5077CrossRefGoogle Scholar
  86. 86.
    Memming R, Tolle H J, Wierenga P E. Properties of polymeric layers of hydrogenated amorphous carbon produced by a plasmaactivated chemical vapour deposition process II: Tribological and mechanical properties. Thin Solid Films, 1986, 143(1): 31–41CrossRefGoogle Scholar
  87. 87.
    Pappas D L, Hopwood J. Deposition of diamondlike carbon using a planar radio frequency induction plasma. Journal of Vacuum Science and Technology Part A, 1994, 12(4): 1576–1582CrossRefGoogle Scholar

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© Higher Education Press and Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.School of EngineeringUniversity of South AustraliaMawson LakesAustralia
  2. 2.Future Industries InstituteUniversity of South AustraliaMawson LakesAustralia
  3. 3.Department of Electrical Engineering and ElectronicsUniversity of LiverpoolLiverpoolUK
  4. 4.Material Science InstituteLancaster UniversityLancasterUK

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