On the importance of ions and ionmolecule reactions to plasma surface interface reactions, journal of the american society for mass spectrometry, 2002, pp. A plasma is a highly reactive gas which contains neutral, excited and ionized. Plasma deposition of fluorocarbon thin films from cc4f8 using. Plasma polymerization or glow discharge polymerization uses plasma sources to generate a gas discharge that provides energy to activate or fragment gaseous or liquid monomer, often containing a vinyl group, in order to initiate polymerization.
This book provides a basic and thorough presentation of. In this regard, styrene monomer is often preferred in the case of plasma polymerization because of its high organic character as well as high vapor pressure. Gas phase reactions for polymerization solid particles were observed in fluorocarbon c4f8 plasmas applied to semiconductor. Polymers formed from this technique are generally highly branched and highly crosslinked, and adhere to solid surfaces well. Note that use of h2 in a plasma containing cl2 or bcl3 can. Radical kinetics for polymer film deposition in fluorocarbon c4f8, c3f6 and c5f8 plasmas by k takahashi, a itoh, t nakamura and k tachibana no static citation data no static citation data cite. Plasma polymerization of octafluorocyclobutane and. The densities of large polymers increase with increasing size of the parent gas. Polymerization of fluorocarbons in reactive ion etching. Memsii lecture 3 dry etching ii university of florida.
Westwood found that the structure of plasma polymers is more regularly and defined in the sense of classic polymers the lower the power input to the plasma a. In the plasma polymerization process, a monomer gas is pumped into a vacuum chamber where it is polymerized by a plasma to form a thin, clear coating. A hybrid modeling study shuxia zhao,1,2 yuru zhang,1,2 fei gao,1 younian wang,1 and annemie bogaerts2 1school of physics and optoelectronic engineering, dalian university of technology, dalian 116024. Under certain process conditions, plasma polymerization of fluorocarbons on structured silicon samples shows two distinctive effects. Knes 4 1 fraunhofer institute for interfacial engineering and biotechnology, nobelstr. In these plasmas polymerization occurs readily and molecules containing up to ten carbon atoms the mass limit of the mass spectrometer. Plasma polymerization aims to bridge the conceptual gap between the academic and practical approaches to plasma polymerization and highlights the significance of plasma polymerization in materials science and technology.
Therefore, it is necessary to enhance the plasma energy to synthesize highdensity conductive polymer nanoparticles with singlecrystallinity as the active layers for gas sensors on various substrates at room temperature. Solid particle production in fluorocarbon plasmas ii. Publishers pdf, also known as version of record includes final page. Another approach is to use chemical dry etching cde of si3n4 with mixtures rich in o2n2 1. Plasma chemistry and reaction mechanism for modeling of arcc4f8o2 discharges. It is converted to a gas in an evaporator and is pumped into the vacuum chamber. Octafluorocyclobutane, or perfluorocyclobutane, c4f8, is a compound of carbon and fluorine used in the production and processing of semiconductor materials and devices, for example as a deposition gas and etchant. Curie university enscp 11 rue picrre ct maric curie 7523 1 paris cedex 05 abstract. Gallen, switzerland plasma polymerization enables the deposition of thin coatings on all kinds of substrates using electrical monomer discharges. Plasma polymerization of fluorinated monomers on mesoporous. A simple plasma polymerization method was used for the preparation of smart copolymer coatings with tunable and reversiblyswitchable wetting properties in various ph environments.
Plasma polymerization of acrylic acid onto polystyrene by. The plasma copolymerization of ethylene et and tetrafluoroethylene tfe was investigated by means of ir and xps analyses. The effect of the o2ar mixing ratio in cf4o2ar and c4f8 o2ar inductively coupled plasmas with a 50% fluorocarbon gas content on plasma parameters and active species densities, which influence. To investigate the mechanism of c 4 f 8 dissociation in parallelplatetype plasma, we used several of the latest diagnostic tools and made extensive measurements of electrons, radicals, and ions under conditions that greatly suppressed the effects of plasma surface interaction. Request pdf solid particle production in fluorocarbon plasmas ii. The thermal stability of ppfc film was improved with substrate temperature. Peel force and demolding status are used to determine if delamination is successful. Property of plasmapolymerized fluorocarbon film in. Bulk plasma fragmentation in a c4f8 inductively coupled. For radicaldominated discharges the reaction parameter power input per gas flow. Jun 30, 2015 a hybrid model is used to investigate the fragmentation of c 4 f 8 inductive discharges. This gas has become available on an industrial scale only recently and we felt the need to increase the data in our possession on its behavior both in the plasma chamber and in the gas delivery systems. Comparison of c4f6ar and c4f8 ar discharges a gas phase and surface chemistry study of.
Atmospheric pressure plasma polymerization using double. Deposition of thin films by plasma polymerization for. On the other hand the low plasma power induced the inclusion of. The plasma polymerization of two fluorocarbon compounds octafluorocyclobutane c. Plasma polymerization depends on monomer flow rate, system pressure and discharge power among other variable parameters such as the geometry of the system, the reactivity of the starting mono. The microporous composite membranes with a hydrophilic layer sandwiched between two. Request pdf irregular film thickness distribution in c4f8 inductively coupled plasma polymer deposition under certain process conditions, plasma polymerization of fluorocarbons on structured. The widerange and tunable wetting properties by coordination of composition, functionality, and morphology using straightforward protocol open up a potential door. The complete surface kinetics model was previously developed, incorporated, and tested for accuracy within the simulator as reported in the companion paper guo et al. Discussion on plasma polymerization mechanism in 1971, a. Nanoscale selective area atomic layer deposition of tio2. Investigation of surface polymerization on silicon exposed to.
The passivation step used in the bosch process alternating etching and deposition steps to perform deep anisotropic silicon etching has been examined in detail. Whether youve loved the book or not, if you give your honest and detailed thoughts then people will find new books that are right for them. Pdf controlled surface wettability by plasma polymer 2. The chain polymerization process occurs with the assistance of plasma energy during plasma polymerization and this plasma energy is used to activate electrons, ions and radicals. Evaluating the performance of cc4f8, cc5f8, and c4f6 for. Plasma rie etching birck nanotechnology center fundamentals and applicationsfundamentals and applications 1. Plasma polymerization of c4f8 passivation layer deposited on silicon was necessary to allow for ease of demolding pdms. Figure 5 summarizes the results of this study, and an evaluation of the chemical composition of the polymer film by xray photoelectron spectroscopy xps.
Pulsed plasma polymerization of benzaldehyde for retention. Vasenkova university of illinois, department of electrical and computer engineering, 1406 west green street. The binding energy of the cfcf n pea k indicated that the component peak was, in fact, due to cfcf. Plasma polymerization takes place in a low pressure and low temperature plasma that is produced by a glow discharge through an organic gas or vapor. Plasma chemistry and reaction mechanism for modeling of arocc4f8oo2 discharges alex v. This paper shows the systematic study on the property of plasmapolymerized fluorocarbon ppfc film formed by a capacitive couplingtype plasma polymerization equipment using a mixture of ch 4 c 4 f 8 gas. Other readers will always be interested in your opinion of the books youve read. The cw and pw plasma polymerization mechanism difference is following figure. Plasma functionalization of foiles and technical textiles with specific tunable wetting behavior m. In this articlc surfacc trcatmcnt of polymcrs by both surfacc modification and plasma. This paper shows the systematic study on the property of plasma polymerized fluorocarbon ppfc film formed by a capacitive couplingtype plasma polymerization equipment using a mixture of ch 4 c 4 f 8 gas. Pulsed plasma polymerization of benzaldehyde for retention of.
Fabrication of hydrophobic films from ofcb monomer by plasma. Plasma polymerization occurs at both low pressure and atmospheric pressure. To better understand the performance differences between c c4f8, c4f6, and cc5f8, we performed a number of characterization studies to learn more about how these molecules. It is able to combine very high performance with a benign environmental effect. Plasma deposition of fluorocarbon thin films from cc4f8 using pulsed. These measurements showed that the amount of light fluorocarbon radicals and ions increased with increasing electron. Plasma polymer films examines the current status of the deposition and characterization of fluorocarbon, hydrocarbon and siliconcontaining plasma polymer films and nanocomposites, with plasma polymer matrix. Optical emission analysis of cf4chf3ar plasma etch of oxide.
Plasma polymerization and its applications in textiles. Elemental composition of plasma polymers from c4f8, chf 3 and. Plasma polymerization of csubscript 4fsubscript 8 thin. This selectivity is due to the deposition of a polymer layer, which is then consumed.
Effects of ar and o2 additives on sio2 etching in c4f8based. Exploration of plasmaenhanced chemical vapor deposition as a method for thinfilm fabrication with biological applications milana c. However, the use of high density plasma sources with high cf ratio gas compositions often generates a thick polymer layer and physical damage on the exposed silicon surface during the overetch period. Plasma and surface properties for icps sustained in cc4f8 oar in this section, results from our parametric investigation of plasma properties of icps sustained in ar, o2, and c4f8 ar mixtures with and without static magnetic.
Tunable wettability and phresponsiveness of plasma. Durham etheses an investigation of plasma polymerization. The polymer along the trench bottom must be sufficiently fluorinated, and there must be an adequate supply of cf2 ions and radicals within the plasma to promote. Deposition and composition of polymer films in fluorocarbon. A study 12 described a combination of plasma and photolithographic processes for production of microstructured surfaces. Investigation of fluorocarbon plasma deposition from c. Film properties are determined using fourier transform infrared ftir. Pulsed plasma polymerization of benzaldehyde is used to produce thin films containing aldehyde functional groups. Fluorocarbon plasma etching is still the foremost process for obtaining. This gas has become available on an industrial scale only recently and. Controlled surface wettability by plasma polymer surface. Plasma deposition, treatment, and etching of polymers, edited by r. Cfcf n and cf2 groups were greatly reduced in intensity in the copolymer. Perfluoroisobutylene is generated during the thermal decomposition of polytetrafluoroethylene4.
To investigate the mechanism of c4f8 dissociation in parallelplatetype plasma, we used several of the latest diagnostic tools and made extensive measurements of electrons, radicals, and ions unde. First, the growth rate at a certain depth inside the trenches is considerably larger than at the shoulders, the trench bottom or other areas of the sidewall. Plasma treatment and polymerization are important technologies for this purpose. General trend in the evolution of rie chemistries for anisotropic etching of sio2. To investigate the mechanism of c4f8 dissociation in parallelplatetype plasma, we used several of the latest diagnostic tools and made extensive measurements of electrons, radicals, and ions under conditions that greatly suppressed the effects of plasma surface interaction. Polymethylmethacrylate pmma, polyvinylpyrrolidone pvp, and octafluorocyclobutane c4f8 were the polymeric materials studied where pmma and pvp were deposited using spin coating and c4f8 was grown using inductively coupled plasma icp polymerization. Bulk plasma fragmentation in a c 4f 8 inductively coupled plasma. Plasma polymerization of c4f8 thin film on high aspect ratio. Plasma polymerization and surface treatment of polymers f. Different process parameters for plasma polymerization e. Plasma surface modification and plasma polymerization crc. The effects of hmdso plasma polymerization on physical, lowstress mechanical and surface properties of wool fabrics fabio rombaldoni, raffaella mossotti, alessio montarsolo, roberto demichelis, riccardo innocenti, giorgio mazzuchetti consiglio nazionale delle ricerche istituto per lo studio delle macromolecole. Tunable surface chemistry and wettability of octafluorocyclobutane and acrylic acid copolymer combined ldpe substrate by pulsed plasma polymerization.
Plasmapolymerization of hmdso using an atmospheric. Polymer formation in plasma polymerization conventional, molecular plasma polymerization, atomic competitive ablation and polymerization cap plasma sensitivity of elements dc discharge polymerization field effects influence of wall contamination. Plasma polymerization and surface treatment of polymers. Perfluoroisobutylenes production and use as a synthetic intermediate for the production of polymeric materials1 and use in the etching process for seimiconductors2 may result in its release to the environment through various waste streamssrc. The effects of pulse peak power, pulseon time, duty cycle, and monomer pressure on film composition, especially aldehyde functional groups, and surface polarity are examined. It introduces plasma polymerization process diagnostics such as optical emission spectroscopy oes, aoes, and describes special.
Exploration of plasmaenhanced chemical vapor deposition as a. Investigation of surface properties of fluorocarbon films. Polymerization of fluorocarbons in reactive ion etching plasmas. Response surface method is employed to provide insights on how changes in coil power, passivating time and gas flow conditions affect plasma polymerization of csubscript 4fsubscript 8.
Once the growth of a chain is initiated by formation of an active center, chain propagation is usually rapid by addition of a sequence of monomers. Indeed, the resulting reactive species are crucial for the optimization of the sibased etching process, since they determine the mechanisms of fluorination, polymerization, and sputtering. The effect of pressure, inductively coupled plasma power, temperature, flow rate, and bias power on both deposition rate and film composition has been explored over a relatively wide range. The property of plasmapolymerized fluorocarbon film in. Tutorial on plasma polymerization deposition of functionalized films mawson institute. Conductive polymer synthesis with singlecrystallinity via. Request pdf fluorocarbonbased plasma etching of sio2. The deposition rates for plasma ettfe copolymers, when plotted versus mol %. Polymerization yields finely divided, stable latexes and dispersions to be used directly in coatings, paints, and adhesives. The source is operated with argon as working gas at a flow rate of 6 slm and 10100 sccm admixtures of the respective monomer. Surface modification of carbon nanofibers and graphene.
Plasma polymer films world scientific publishing company. Ar plasma etching was simulated using a threedimensional monte carlo profile simulator. They observed static water contact angle swca is higher for c2f6 and 399 c3f8 polymer coatings by pw plasma polymerization, but swca of c4f8 plasma polymer coating is 400 higher for cw plasma polymerization as shown in tab. Styrene is very important from the technological point of view and is widely investigated 47. Jun 01, 2003 it is able to combine very high performance with a benign environmental effect. Membrane surface modification by plasma polymerization of ethylenediamine for fractination of saccharides haci ali gulec1, arzu topacli 2, cafer topacli, yasin sen3, nedim albayrak1, mehmet mutlu3 1 department of food engineering, yuzuncu yil university, 65080 van, turkey. Plasma polymerization of acrylic acid onto polystyrene by cyclonic plasma at atmospheric pressure yijan chang, chinho lin, and chun huang department of chemical engineering and materials science, yuan ze university, chungli 32003, taiwan. Irregular film thickness distribution in c4f8 inductively. A new straightforward protocol for the fabrication of. Mechanism of c4f8 dissociation in parallelplatetype plasma. Synthesis and characterization of plasma polymerized. Abstract hexafluoro1,3butadiene c 4 f 6 is a relatively new etch gas for the manufacturing of semiconductor devices, especially in critical etch processes that need high aspect ratios and selectivity. Therefore, the control of characteristics of the formed polymer layers, which is a main factor in obtaining high selectivity to. Plasma functionalization of foiles and technical textiles.
In a first step, a layer which is nonadhesive towards cells and proteins was obtained by pulsed plasma polymerization of diethylene glycol dimethyl ether monomer ppeolike. In this paper, hydrophilic microporous cellulose nitrate membranes have been surface. Poh, yee cheong lam and mary beeeng chanpark download pdf 664 kb. Plasma copolymerization of ethylene and tetrafluoroethylene. In chaingrowth or chain polymerization, the only chainextension reaction step is the addition of a monomer to a growing chain with an active center such as a free radical or ion. If the adhesion forces between the silicone rubber and the wafer were too high, the silicone rubber would be stuck in the trenches of the wafer and the mold would be rendered useless for subsequent usage. In contrast to rie, the synergistic effect of ion bombardment, which is. On the importance of ions and ionmolecule reactions to. Pulsed plasma polymerization of precursors containing long perfluoroalkyl chains can lead to the formation of structurally welldefined low surface energy films.
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