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Tutorial on Plasma Polymerization Deposition of Functionalized Films

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Tutorial on Plasma Polymerization Deposition of Functionalized Films Tutorial on Plasma Polymerization Deposition of Functionalized Films A. Michelmore, D.A. Steele, J.D. Whittle, J.W. Bradley, R.D. Short University of South Australia Based upon review article RSC Advances, 2013, 3, 13540-13557 Mawson Institute Plasma – Surface Interactions • For plasma polymerisation, what happens at the surface is key. • This is the intersection of plasma physics and plasma chemistry. Mawson Institute Some basic terms and concepts • Plasma = electrons, ions, radicals, neutrals (and photons) • Particles are not in equilibrium • Two important concepts: unit of energy (eV) and average energy per molecule, Emean • 1 eV is KE gained by electron when loses 1V of PE and conversion to K: 1.6 헑 10⁻¹⁹J 1eV = = 11,600K 1.38 푥 10⁻²³ J K ⁻¹ • eV useful as not only defines temperature, but also DV species have energy to overcome • Amount of energy per molecule: 퐸푚푒푎푛=훾 푃/휙 where 훾 is the duty cycle for pulsed plasmas, given by: 훾=ton /((ton + toff ) For continuous wave plasma, this term reduces to 1 Mawson Institute What happens at a surface? • Does a surface affect the plasma …… YES! • First described by David Bohm in 1949 • Often not even considered in depositing plasmas. Mawson Institute Surfaces change everything! • Traditional view of plasma polymerization does not account for plasma physics at surfaces • Assume ions not important because low ion density compared to neutral/radical density in the plasma ….WRONG! • We need some basic plasma physics to proceed Mawson Institute Imagine a space plasma, with an imaginary plane A Net flux of charged particles through an imaginary plane (left) Mawson Institute A Mawson Institute Now imagine putting a solid surface in the plasma (e.g. like a chamber wall or substrate) B Net flux of charged particles to a solid surface (right) Mawson Institute B Formation of (charge density) sheath • There is a net flow of negative charge to the surface – Initially much higher electron flux at surface (hotter and lower mass) – The surface develops a negative potential compared to the plasma – All surfaces in contact with the plasma develop a sheath Electrons start to be repelled from surface Positive ions start to be attracted to surface No glow in this region Extends up to a few mm from surface – Surface charges negatively until ion flux = electron flux (steady state) – Typical potential difference of ~10 – 50V - Positive ions accelerated across sheath to the surface - Ion energies quite large when striking surface (>10eV) - Electrons decelerated (only high energy e-s get through) Mawson Institute Within the sheath, ions convert electrical potential energy into kinetic energy as they approach the negatively charged surface. For ion energy conservation: ½ M v(푥)²=½M v²-eV(푥) Schematic of the sheath and pre-sheath adjacent to a wall in contact with a plasma phase A Michelmore et al , RSC Advances, 2013, 3, 13540 Mawson Institute Presheath – Between the plasma and the sheath – For sheath to be stable region of positive space charge: • Local electron density < local ion density – But at the sheath edge • ion density = electron density (Boundary condition) Mawson Institute The Bohn Criterion Solution for these conditions to exist: D. Bohm (1949) ions enter sheath with velocity > acoustic velocity ퟏ ퟐ ퟏ 풌푻풆 풗풊 = 풌푻풆 풎 풂풏풅 푱풊 = 풆풙풑 − 풏풊 ퟐ 풎풊 푱풊 ퟏ 푻풆 Ion flux increased by = ퟐπ 풆풙풑 − due to the surface! 푱풕 ퟐ 푻풊 So, if Ti ~300K, enhanced ion flux proportional to Te! If Te = 30,000K, ion flux increased ~15x due to the surface! Mawson Institute Measuring Ion Flux • At equilibrium, ion flux = electron flux – No net current • Need to exclude electron current to measure ion current – Apply negative voltage Mawson Institute Measuring Ion Flux • Braithwaite ion flux probe design – Apply RF pulse to a surface (~10ms) – Surface develops negative bias – Chop RF pulse, and measure probe voltage vs time – Slope proportional to ion current t V RF Pulse on RF chopped and measure V vs time Mawson Institute Measuring Ion Flux • Sobelewski method (1998) – Uses internal RF electrode – Measure electrode current at bottom of RF sweep RF Voltage Measure current at min. V and average Mawson Institute Measuring Ion Flux - HMDSO 9 s) 8 2 7 ions/m 6 18 5 0.5mT 4 1mT 3 1.5mT 2 1 Positive Ion Ion Flux (10 Positive 0 0 10 20 30 40 50 RF Power (W) Ion flux increases with RF power, and decreases with pressure Mawson Institute Ion Energy Energy of ions arriving at a grounded surface can be measured with Plasma Mass Spectrometers Ions undergoing collisions in the sheath, lose energy Counts 0 5 10 15 20 25 30 35 40 45 50 Ion energy (eV) Mawson Institute Summary • Neutrals/radicals diffuse to surfaces by thermal motion • Only hot electrons can impact surface, with reduced energy • Ions are accelerated to surfaces by the sheath – Increased flux (approx. 15x higher than thermal flux) – Increased ion energy (typically 20eV) Mawson Institute .
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