Remote plasma enhanced cyclic etching of a cyclosiloxane polymer thin film

The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.

Investigation of working pressure on the surface roughness controlling technology of glow discharge polymer films based on the diagnosed plasma

The effects of working pressure on the component, surface morphology, surface roughness, and deposition rate of glow discharge polymer （GDP） films by a trans-2-butene/hydrogen gas mixture were investigated based on plasma characteristics diagnosis. The composition and ion energy distributions of a multi-carbon （CaHs/H2） plasma mixture at different working pressures were diagnosed by an energy-resolved mass spectrometer （MS） during the GDP film deposition process. The Fourier transform infrared spectroscopy （FT-IR）, field emission scanning electron microscope （SEM） and white-fight interferometer （WLI） results were obtained to investigate the structure, morphology and roughness characterization of the deposited films, respectively. It was found that the degree of ionization of the C4H8/H2 plasma reduces with an increase in the working pressure. At a low working pressure, the C-H fragments exhibited small-mass and high ion energy in plasma. In this case, the film had a low CH3/CH2 ratio, and displayed a smooth surface without any holes, cracks or asperities. While the working pressure increased to 15 Pa, the largest number of large-mass fragments led to the deposition rate reaching a maximum of 2.11 #m h-1, and to hole defects on the film surface. However, continuing to increase the working pressure, the film surface became smooth again, and the interface between clusters became inconspicuous without etching pits.

Hydrophobic coating of surfaces by plasma polymerization in an RF plasma reactor with an outer planar electrode:synthesis,characterization and biocompatibility

This paper presents the plasma polymerization of poly（hexafluorobutyl acrylate）（PHFBA） thin films on different substrates in an RF plasma reactor with an outer planar electrode. This reactor configuration allows？large area uniformity and fast processing times. Deposition rates of up to60 nm min-1were observed. The influence？of plasma power and substrate temperature on the？deposition rate, structure and wettability of the as-deposited films was？investigated. It was observed that better hydrophobicity was obtained at high plasma power and in low temperature conditions. PHFBA thin films deposited on electrospun poly（acrylonitrile） fiber mats under such conditions resulted in superhydrophobic surfaces with？contact angle values greater than 150°.In？vitro cell studies using human epithelial cells demonstrated the non-toxic nature of the？plasma-polymerized PHFBA films.

Electron density measurement of laser-induced epoxy fiber reinforced polymer plasma

Interferograms of laser-induced epoxy fiber reinforced polymer plasmas are obtained through aMach-Zehnder interferometry system. An improved digital double-exposure Fourier method is applied to extractinitial wrapped phases from interferograms, and then an improved phase unwrapping algorithm based on a maskand a branch-cut method is proposed to solve the problem of phase unwrapping. After the inverse Abel transfor-mation of the unwrapped phase, spatial distributions of the electron density of laser-induced epoxy fiber rein-forced polymer plasma at various delays are acquired. Results show that the measured electron density of theplasma is mainly distributed on the order of 10^18 cm^3. The experiment also indicates that the total amount oflaser plasma electrons changes slightly within the recorded time and the change of the electron density is approx-imately inversely proportional to the change of the plasma volume.

Investigation of the performance of a pilot-scale barrel atmospheric plasma system for plasma activation of polymer particles

This study reports the development and performance of a pilot-scale barrel atmospheric plasma reactor for the atmospheric plasma activation treatment of polymer particles. The polymer particles treated included acrylonitrile butadiene styrene(ABS) and polypropylene(PP). These particles had diameters in the range of 3–5 mm. The initial studies were carried out using a laboratory-scale barrel reactor designed to treat polymer particle batch sizes of 20 g. A pilot-scale reactor that could treat 500 g particle batch sizes was then developed to facilitate pre-industrial-scale treatments. The effect of operating pulse density modulation(PDM) in the range 10%–100% and plasma treatment time on the level of activation of the treated polymers were then investigated. ABS revealed a larger decrease in water contact angle compared with PP after plasma treatment under the same conditions. The optimal treatment time of ABS(400 g of polymer particles) in the pilot-scale reactor was 15 min. The plasma-activated polymer particles were used to fabricate dog-bone polymer parts through injection molding.Mechanical testing of the resulting dog-bone polymer parts revealed a 10.5% increase in tensile strength compared with those fabricated using non-activated polymer particles.

Polymer Surface Treatment by Atmospheric Pressure Low Temperature Surface Discharge Plasma:Its Characteristics and Comparison with Low Pressure Oxygen Plasma Treatment

The polymer treatment with a low-temperature plasma jet generated on the atmospheric pressure surface discharge （SD） plasma is performed. The change of the surface property over time, in comparison with low pressure oxygen （O2） plasma treatment, is examined. As one compares the treatment by atmospheric pressure plasma to that by the low pressure O2 plasma of PS （polystyrene） the treatment effects were almost in complete agreement. However, when the atmospheric pressure plasma was used for PP（polypropylene）, it produced remarkable hydrophilic effects.

NH_3 Plasma Surface Treatments of Engineering Fluoropolymers: A Way to Enhance Adhesion of Ni or Cu Thin Films Deposited by Electroless Plating

This paper describes the electroless Ni or Cu plating of some fiuoropolymer substrates through a tin-free activation process. Materials subjected to surface metallization are commercial Teflon() FEP, Nafion(), ACLAR() and LaRCTM-CP1 thin films which have recently gained a large scientific and technological interest due to their excellent thermal, chemical, mechanical and dielectric properties. The original approach implemented in the present work involves: (i)the grafting of nitrogen-containing functionalities on the polymer surfaces through plasma treatments in ammonia, (ii) the direct catalysis of the so-modified surfaces via their immersion in a simple acidic PdCl2 solution (i.e. without using a prior surface sensitization in an acidic SnCl2 solution), and finally (iii) the electroless metallization itself. However, prior to the immersion in the industrial plating baths, the chemical reduction of the Pd+2 species (species covalently tethered on the nitrogen-containing groups) to metallic palladium (PdO) is shown to be a key factor in catalyzing the electroless deposition initiation. This is made by immersion in an hypophosphite (H2PO2-) solution. Wettability measurements and X-ray photoelectron spectroscopy (XPS) experiments are used to characterize every surface modification step of the developed process. A cross-hatch tape test was used to asses the adhesion strength of the electroless films that is shown qualitatively good. In addition, a fragmentation test was developed in combination with electrical measurements. Its use allows to distinguish different adhesion levels at the metal/polymer interface and to evidence the influence of some processing parameters.

Effect of Oxygen on Surface Properties and Drug Release Behavior of Plasma Polymer of n-Butyl Methacrylate

The effects of oxygen on the chemical structure, morphology, hydrophilicity and drug release behavior of radio-frequency plasma poly n- butyl methacrylate （PPBMA） thin film were carded out for the first time. ATR-FTIR and XPS showed that oxygen had little influence on the chemical structure and composition of PPBMAs, which did not agree with the thought that the presence of oxygen gas would increase the oxidized carbon functionalities in the plasma polymer. SEM and static contact angle measurement indicated that in case of deposition with oxygen, the smoothness and hydrophilicity of PPBMA were dramatically improved. The drug release behavior showed that drug release from the PPBMA coating without oxygen was biphasic patterns, while from PPBMA coating with oxygen was Higuchi release. These results were helpful for the design and tailoring of the PPBMA polymer film and other of plasma polymers film, but could provide a new idea for the drug release controlled form.

PLASMA POLYMERIZED ORGANOSILANES AS A PROTECTIVE COATING ON METAL

Polymer-metal oxane bonds (M-O-Si) can be created in the form of tight networks by silane plasma polymerization directly on the metal (e.g. copper) substrates. In this paper the structure and properties of the plasma-deposited organosilane polymers, the corrosion performance of such coating system on copper substrates were investigated.

Deposition of Polymer Thin Film Using an Atmospheric Pressure Micro-Plasma Driven by Dual-Frequency Excitation

Polymer thin film deposition using an atmospheric pressure micro-plasma jet driven by dual-frequency excitations is described in this paper. The discharge process was operated with a mixture of argon （6 slm） and a small amount of acetone （0-2100 ppm）. Plasma composition was measured by optical emission spectroscopy （OES）. In addition to a large number of Ar spectra lines, we observed some spectra of C, CN, CH and C2. Through changing acetone content mixed in argon, we found that the optimum discharge condition for deposition can be characterized by the maximum concentration of carbonaceous species. The deposited film was characterized by scanning electron microscopy （SEM） and X-ray photoelectron spectroscopy （XPS） and Fourier transform infrared （FTIR） spectroscopy. The XPS indicated that the film was mostly composed of C with trace amount of O and N elements. The FTIR suggested different carbon-containing bonds （-CHx, C=O, C=C, C-O-C） presented in the deposited film.

Comparison of Surface Modification of CR-39 Polymer Film Using RF and DC Glow Discharges Plasma

Surfaces of optical elements are deposited by antireflection coatings (ARCs) to decrease the reflection of light. Surface needs treatment before depositing the ARC one of treatment processes by plasma for adhesion improvement and surface hardening. A comparison of RF and DC glow discharges treated CR-39 polymer films gives insight into the mechanism of these surface processes. The surface properties of the plasma-treated samples are examined by microscopy techniques include contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared (IR) spectroscopy and refractive index measurements. Results show that the plasma treatment modifies the polymer surface in both composition and morphology. It is found that the surface wettability is enhanced after plasma treatment. It is found that, RF plasma is more effective than DC plasma in CR-39 surface modification, as it implants more oxygen atoms into the surface and makes the contact angle declining to a lower level.

Helium Plasma Effects on Polymer Surfaces:from Plasma Parameters and Surface Properties towards Bioengineering Applications

Plasma treatment is necessary to optimize the performance of biomaterial surfaces.It enhances and regulates the performance of biomaterial su rfaces,creating an effective interface with the human body.Plasma treatments have the ability to modify the chemical com position and physical structu re of a surface while leaving its properties unaffected.They possess the ability to modify material su rfaces,eliminate contaminants,conduct investigations on cancer therapy,and facilitate wound healing.The subject of study in question involves the integration of plasma science and technology with biology and medicine.Using a helium plasma jet source,applying up to 18 kV,with an average power of 10 W,polymer foils were treated for 60 s.Plasma treatment has the ability to alter the chemical composition and physical structure of a su rface while maintaining its quality.This investigation involved the application of helium plasma at atmospheric pressure to polyamide 6 and polyethylene terephthalate sheets.The inquiry involves monitoring and assessing the plasma source and polymer materials,as well as analyzing the impacts of plasma therapy.Calculating the mean power of the discharge aids in assessing the economic efficacy of the plasma source.Electric discharge in helium at atmospheric pressure has beneficial effects in technology,where it increases the surface free energy of polymer materials.In biomedicine,it is used to investigate cytotoxicity and cell survival,particularly in direct blood exposure situations that can expedite coagulation.Comprehending the specific parameters that influence the plasma source in the desired manner for the intended application is of utmost im portance.

Plasma Induced Grafting of PMMA onto Titanium Dioxide Powder

Grafting of polymer of methyl methacrylate （PMMA） onto titanium dioxide powder is investigated in this paper. The graft polymerization reaction is induced by dielectric-barrier- discharge produced N2 plasma treatment of titanium dioxide surfaces. IR, XPS and TGA results show that PMMA is grafted onto the surfaces of titanium dioxide powder. And crystal structure of the titanium dioxide powder observed with XRD spectra is unchanged after plasma graft polymerization.

Recent progress on non-thermal plasma technology for high barrier layer fabrication

This review describes the application of non-thermal plasma（NTP） technology for high barrier layer fabrication in packaging area.NTP technology is considered to be the most prospective approaches for the barrier layer fabrication over the past decades due to unpollution,high speed,low-costing.The applications of NTP technology have achieved numerous exciting results in high barrier packaging area.Now it seemly demands a detailed review to summarize the past works and direct the future developments.This review focuses on the different NTP resources applied in the high barrier area,the role of plasma surface modification on packaging film surface properties,and the deposition of different barrier coatings based on NTP technology.In particular,this review emphasizes the cutting-edge technologies of NTP on interlayer deposition with organic,inorganic for multilayer barriers fabrication.The future prospects of NTP technology in high barrier film areas are also described.

The Effects of Gas Composition on the Atmospheric Pressure Plasma Jet Modification of Polyethylene Films

Polyethylene （PE） films are treated using an atmospheric pressure plasma jet （APPJ） with He or He/O2 gas for different periods of time. The influence of gas type on the plasma polymer interactions is studied. The surface contact angle of the PE film can be effectively lowered to 58° after 20 s of He/O2 plasma treatment and then remains almost unchanged for longer treatment durations, while, for He plasma treatment, the film surface contact angle drops gradually to 47° when the time reaches 120 s. Atomic force microscopy （AFM） results show that the root mean square （RMS） roughness was significantly higher for the He/O2 plasma treated samples than for the He plasma treated counterparts, and the surface topography of the He/O2 plasma treated PE films displays evenly distributed dome-shaped small protuberances. Chemical composition analysis reveals that the He plasma treated samples have a higher oxygen content but a clearly lower percentage of COO than the comparable He/O2 treated samples, suggesting that differences exist in the mode of incorporating oxygen between the two gas condition plasma treatments. Electron spin resonance （ESR） results show that the free radical concentrations of the He plasma treated samples were clearly higher than those of the He/O2 plasma treated ones with other conditions unchanged.

All-organic modification coating prepared with large-scale atmospheric-pressure plasma for mitigating surface charge accumulation

The surface charge accumulation on polymers often leads to surface flashover.Current solutions are mainly based on the introduction of inorganic fillers.The high-cost process and low compatibility remain formidable challenges.Moreover,existing researches on all-organic insulation focus on capturing electrons,contrary to alleviating charge accumulation.Here,an all-organic modification coating was prepared on polystyrene(PS)with the large-scale atmospheric-pressure plasma,which exhibits outperformed function in mitigating surface charge accumulation.The surface charge dissipation rate and surface conductivity are promoted by about 1.37 and 9.45 times,respectively.Simulation and experimental results show that this all-organic modification coating has a smaller electron affinity potential compared with PS.The decrease of electron affinity potential may result in accelerated surface charge decay of PS,which has never been involved in previous works.Moreover,this coating also has good reliability in a repeated surface flashover.This facile and large-scale approach brings up a novel idea for surface charge regulation and the manufacture of advanced dielectric polymers.

PLASMA MODIFICATION OF POLYPROPYLENE SURFACES AND GRAFTING COPOLYMERIZATION OF STYRENE ONTO POLYPROPYLENE

The surface of polypropylene （iPP） is modified with glow discharge plasma of Ar, so that the modified surfaces of iPP films are obtained. The studies of scanning electron microscopy （SEM） show the surface etching pattern of iPP films. The chemical structures of iPP films are confirmed by X-ray photoelectron spectroscopy （XPS） and Fourier transform infrared （FTIR） spectroscopy. The wetting properties of modified surfaces of iPP films are characterized by contact angle, and the free energy of surfaces is calculated. The free radical of modification surfaces of iPP is measured by chemical method. The surfaces of iPP are achieved with Ar plasma treatment followed by grafting copolymerization with styrene （St） in St. The grafting polymer of St onto iPP is characterized by FTIR. The grafting rate is dependent on plasma exposure time and discharge voltage. The studies show that homopolymerization of St is undergone at the sane time during the graftingcopolymerization of St onto/PP.

等离子体改性多孔聚合物材料负载银纳米粒子的抗菌性能

在材料表面均匀稳定地负载纳米银粒子并提高其抗菌性能是目前面临的一项挑战。为此利用纳秒脉冲放电预处理结合化学浸渍法制备了一种纳米银-多孔聚合物复合材料。利用原子力显微、X射线光电子能谱测试分析了等离子体改性前后多孔聚合物材料表面物理性能和化学成分的变化。利用扫描电子显微镜和X射线光电子能谱分析了纳米银在多孔聚合物材料表面的分布情况。以大肠杆菌和白色念球菌为测试菌种,测试在不用放电处理时间、脉冲峰值电压、硝酸银浓度以及作用时间下纳米银-多孔聚合物复合材料的抗菌性能。结果表明,等离子体改性时间为20min、脉冲峰值电压30kV的条件下,在10mmol/L的硝酸银溶液中浸渍得到的复合材料在作用时间为5h时,对大肠杆菌和白色念球菌的杀菌率仍高达99.3%和98.9%,展现出良好的抗菌效果。

Multifunctional antimicrobial chlorhexidine polymers by remote plasma assisted vacuum deposition

Novel antibacterial materials for implants and medical instruments are essential to develop practical strategies to stop the spread of healthcare associated infections. This study presents the synthesis of multifunctional antibacterial nanocoatings on polydimethylsiloxane (PDMS) by remote plasma assisted deposition of sublimated chlorhexidine powders at low pressure and room temperature. The obtained materials present effective antibacterial activity against Escherichia coli K12, either by contact killing and antibacterial adhesion or by biocide agents release depending on the synthetic parameters. In addition, these multifunctional coatings allow the endure hydrophilization of the hydrophobic PDMS surface, thereby improving their biocompatibility. Importantly, cell-viability tests conducted on these materials also prove their non-cytotoxicity, opening a way for the integration of this type of functional plasma films in biomedical devices.

Non-thermal plasma assisted polymer surface modification and synthesis:A review

This article reviews the applications of plasma to polymer surface modification and polymer synthesis.Plasma treatment causes changes in morphology,structure and properties of polymers.When polymers are treated using plasma,certain monomers with functional groups can be copolymerized with backbone chain or be loaded on the surface,which would help couple reaction of existing polymer chains,graft monomers onto polymers,immobilize proteins,carry antimicrobial drugs,and enhance cell attachment.Hence,non-thermal plasma process creates unique properties on polymers which allow improved and expanded applications of polymers in food packaging and biotechnology.