Frontiers of Chemical Science and Engineering >
Where physics meets chemistry: Thin film deposition from reactive plasmas
Received date: 08 Jun 2016
Accepted date: 23 Sep 2016
Published date: 29 Nov 2016
Copyright
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.
Key words: thin films; plasma physics; plasma chemistry; functionalization; polymer
Andrew Michelmore , Jason D. Whittle , James W. Bradley , Robert D. Short . Where physics meets chemistry: Thin film deposition from reactive plasmas[J]. Frontiers of Chemical Science and Engineering, 2016 , 10(4) : 441 -458 . DOI: 10.1007/s11705-016-1598-7
1 |
Chatelier R C, Dai L, Griesser H J, Li S, Zientek P, Lohmann D, Chabrecek P U S. Patent, 6623747, <Date>2003-09-23</Date>
|
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): 786–789
|
3 |
Yasuda H. Plasma Polymerization. New York: Academic Press, 1985
|
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): 1023–1032
|
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 carbon-fibercomposites. Composites. Part A, Applied Science and Manufacturing, 1999, 30(1): 49–57
|
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): 5537–5539
|
7 |
Michelmore A, Whittle J D, Short R D, Boswell R W, Charles C. An Experimental and analytical study of an asymmetric capacitively coupled plasma used for plasma polymerization. Plasma Processes and Polymers, 2014, 11(9): 833–841
|
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): 13–20
|
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, 1989
|
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): 181–189
|
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): 119–135
|
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): 6495–6502
|
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): 113–132
|
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): 1717–1725
|
15 |
Michelmore A, Steele D A, Robinson D E, Whittle J D, Short R D. The link between mechanisms of deposition and the physico-chemical properties of plasma polymer films. Soft Matter, 2013, 9(26): 6167–6175
|
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): 2664–2671
|
17 |
Gengenbach T R, Chatelier R C, Griesser H J. Characterization of the ageing of plasma-deposited polymer films: Global analysis of x-ray photoelectron spectroscopy data. Surface and Interface Analysis, 1996, 24(4): 271–281
|
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): 80–87
|
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): 163–170
|
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): 11943–11950
|
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): 2595–2601
|
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): 23086–23091
|
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): 5387–5391
|
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): 817–826
|
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): 15359–15369
|
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): 496–503
|
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: 368–372
|
28 |
Jiang Z, Jiang Z J. Plasma techniques for the fabrication of polymer electrolyte membranes for fuel cells. Journal of Membrane Science, 2014, 456: 85–106
|
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: 831–838
|
30 |
Zhao X Y, Wang M Z, 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): 812–817
|
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: 109–115
|
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): 89–95
|
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): 2647–2656
|
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: 166–173
|
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): 1–7
|
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: 105–114
|
37 |
Ma G Q, Liu Y, Wei S, Sheng J. Surface modification of polypropylene by ethylene plasma and its induced β-form in polypropylene. Chinese Journal of Polymer Science, 2015, 33(5): 669–673
|
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 plasma-treated polymethyl methacrylate surface. Soft Matter, 2014, 10(6): 903–910
|
39 |
Zhang Z G, Zhang T Z, Li J S, Ji Z L, Zhou H M, Zhou X F, Gu N. Preparation of poly(<?A3B2 th=8pt?>L<?A3B2 th?>-lactic acid)-modified polypropylene mesh and its antiadhesion in experimental abdominal wall defect repair. Journal of Biomedical Materials Research Part B, 2014, 102(1): 12–21
|
40 |
Denaro A R, Owens P A, Crawshaw A. Glow discharge polymerization—styrene. European Polymer Journal, 1968, 4(1): 93–106
|
41 |
Westwood A R. Glow discharge polymerization—rates and mechanisms of polymer formation. European Polymer Journal, 1971, 7(4): 363–375
|
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): 13540–13557
|
43 |
Chabert P, Braithwaite N. Physics of Radio-Frequency Plasmas.Cambridge: Academic Press, 2011
|
44 |
Lieberman M A, Lichtenberg A J. Principles of Plasma Discharges and Materials Processing.Chichester: John Wiley and Sons, 1994
|
45 |
Hulburt E O. Atmospheric ionization by cosmic radiation. Physical Review, 1931, 37(1): 1–8
|
46 |
Blanksby S J, Ellison G B. Bond dissociation energies of organic molecules. Accounts of Chemical Research, 2003, 36(4): 255–263
|
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): 870–881
|
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): 13987–13994
|
49 |
Flory P J. Principles of Polymer Chemistry. New York: Cornell University Press, 1953
|
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): 71–81
|
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): 151502
|
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 W A, 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): 767–778
|
53 |
Williams T, Hayes M W. Polymerization in a glow discharge. Nature, 1966, 209(5025): 769–773
|
54 |
Chapman B. Glow Discharge Processes.Chichester: John Wiley and Sons, 1980
|
55 |
Doyle J R. Chemical kinetics in low pressure acetylene radio frequency glow discharges. Journal of Applied Physics, 1997, 82(10): 4763–4771
|
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): 1961–1964
|
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): 2160–2173
|
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): 839–842
|
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): 1363–1370
|
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, 77–86
|
61 |
Vender D, Boswell R W. Numerical modeling of low-pressure RF plasma. IEEE Transactions on Plasma Science, 1990, 18(4): 725–732
|
62 |
Jacobs D C. Reactive collisions of hyperthermal energy molecular ions with solid surfaces. Annual Review of Physical Chemistry, 2002, 53(1): 379–407
|
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): 171501
|
64 |
Truica-Marasescu F, Wertheimer M R. Vacuum-ultraviolet photopolymerisation of amine-rich thin films. Macromolecular Chemistry and Physics, 2008, 209(10): 1043–1049
|
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): 7150–7153
|
66 |
Haller I, White P. Polymerization of butadiene gas on surfaces under low energy electron bombardment. Journal of Physical Chemistry, 1963, 67(9): 1784–1788
|
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): 053304
|
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, 1–33
|
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): 783–802
|
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): 164–170
|
71 |
Hegemann D, Hanselmann B, Blanchard N, Amberg M. Plasma-substrate interaction during plasma deposition on polymers. Contributions to Plasma Physics, 2014, 54(2): 162–169
|
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: 19–44
|
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): 12395–12405
|
74 |
VonKeudell 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): 676–678
|
75 |
McNaught A D, Wilkinson A. IUPAC Compendium of Chemical Terminology, 2nd ed.Oxford: Blackwell Scientific Publications, 1997
|
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): 3907–3912
|
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): 281–297
|
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): 5730–5736
|
79 |
Michelmore A, Whittle J D, Short R D. The importance of ions in low pressure PECVD plasmas. Frontiers in Physics, 2015, 3: 3
|
80 |
von Keudell A. Surface processes during thin-film growth. Plasma Sources Science & Technology, 2000, 9(4): 455–467
|
81 |
Khelifa F, Ershov S, Habibi Y, Snyders R, Dubois P. Free-radical-induced grafting from plasma polymer surfaces. Chemical Reviews, 2016, 116(6): 3975–4005
|
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): 7782–7789
|
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): 32–41
|
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): 4496–4504
|
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): 5070–5077
|
86 |
Memming R, Tolle H J, Wierenga P E. Properties of polymeric layers of hydrogenated amorphous carbon produced by a plasma-activated chemical vapour deposition process II: Tribological and mechanical properties. Thin Solid Films, 1986, 143(1): 31–41
|
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): 1576–1582
|
/
〈 | 〉 |