Surface modification of a liquid‐crystalline polymer for copper metallization

The effects of different surface modifications on the adhesion of copper to a liquid‐crystalline polymer (LCP) were investigated with X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, contact‐angle measurements, and pull tests. High pull‐strength values were achieved when copper was sputter‐deposited onto plasma and reactive‐ion‐etching (RIE)‐pretreated LCP surfaces. The values were comparable to the reference pull strengths obtained with laminated copper on the LCP. The adhesion was relatively insensitive to the employed feed gas in the pretreatments. The surface characterizations revealed that for RIE and plasma treatments, the enhanced adhesion was attributable to the synergistic effects of the increased surface roughness and polar component of the surface free energy of the polymer. However, if the electroless copper deposition was performed on RIE‐ or plasma‐treated surfaces, very poor adhesion was measured. Good adhesion between the LCP substrate and electrolessly deposited copper was achieved only in the case of wet‐chemical surface roughening as a result of the creation of a sufficient number of mechanical interlocking sites, together with a significant loss of oxygen functionalities, on the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 623–636, 2003     

Effects of RF power on BZN thin‐film etching in SF6/Ar using surface analysis

Reactive ion etching (RIE) was used to etch bismuth zinc niobate (BZN) films in SF₆/ Ar plasma as a function of radio frequency (RF) power. Within the RF power range of choice, the etch rate of BZN films increases with increasing RF power. However, when RF power exceeds 200 W, the etch rate of films appears to increase at a slower rate. The structural properties of the BZN films before and after etching were characterized using X‐ray diffraction. As‐deposited film shows a cubic pyrochlore structure with preferential (222) plane orientation, but all the films etched at different reactive ion etching powers exhibit preferential (400) plane orientation. With increasing RF power, the ZnF₂ phase becomes evident. Also, the film surfaces before and after etching were analysed using XPS. Metal fluorides were found to remain on the surface, resulting in varying relative atomic percentages with RF power. Zn‐rich surfaces were formed because low‐volatile ZnF₂ residues were difficult to remove. Bi and Nb can be removed easily through chemical reactions because of their high volatility, whereas Bi–F and Nb–F, which were thought to be present in the form of a metal oxyfluoride, can still be detected using the narrow scan spectra. RF power has an effect on etch reaction through different plasma densities and particle energies, thus resulting in varying compositions and element chemical binding states. RF power also has an effect on the removal of residues. The minimum value of F atomic concentration is achieved at 150 W. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface Modification of Absorbable Magnesium Stents by Reactive Ion Etching

The surface texture and chemistry of WE43 absorbable magnesium stents (AMS) and tube specimens processed by chemical and reactive ion etching (RIE) were investigated. Tube specimens were produced in three different conditions, namely as-received, chemically etched and plasma etched. The results of scanning electron microscopy, atomic force microscopy and energy dispersive X-ray spectroscopy studies showed that plasma etching and cleaning reduced surface roughness by 10 % compared to chemical etching alone, and completely removed surface deposits remaining from the chemical etch process. The same combination of chemical and plasma etching processes was employed to produce AMS. Expansion tests demonstrated uniform stent expansion characteristics and confirmed the viability of the device. The results of this study show that RIE is an effective surface modification technique for absorbable magnesium devices.     

Removal of Ar+ beam‐induced damaged layers from polyimide surfaces with argon gas cluster ion beams

An Ar Gas Cluster Ion Beam (GCIB) has been shown to remove previous Ar⁺ ion beam‐induced surface damage to a bulk polyimide (PI) film. After removal of the damaged layer with a GCIB sputter source, XPS measurements show minor changes to the carbon, nitrogen and oxygen atomic concentrations relative to the original elemental bulk concentrations. The GCIB sputter depth profiles showed that there is a linear relationship between the Ar⁺ ion beam voltage within the range from 0.5 to 4.0 keV and the dose of argon cluster ions required to remove the damaged layer. The rate of recovery of the original PI atomic composition as a function of GCIB sputtering is similar for carbon, nitrogen and oxygen, indicating that there was no preferential sputtering for these elements. The XPS chemical state analysis of the N 1s spectra after GCIB sputtering revealed a 17% damage ratio of altered nitrogen chemical state species. Further optimization of the GCIB sputtering conditions should lead to lower nitrogen damage ratios with the elemental concentrations closer to those of bulk PI. Copyright © 2010 John Wiley & Sons, Ltd.     

Facile Synthesis of High‐Quality Plasma‐Reduced Graphene Oxide with Ultrahigh 4,4′‐Dichlorobiphenyl Adsorption Capacity

High‐quality reduced graphene, termed PG, has been synthesized by a simple, low‐cost, and green plasma approach, and applied as adsorbent to remove 4,4′‐dichloribiphenyl (4,4′‐DCB) from aqueous solutions. As a comparison, the adsorption of 4,4′‐DCB on graphene oxide (GO) and multiwalled carbon nanotubes (MWCNTs) was also studied under the same experimental conditions. PG performs significantly better with regard to 4,4′‐DCB adsorption than GO and MWCNTs, or any reported nanomaterials, with a maximum adsorption capacity (q_max) of 1552 mg g^?1 at pH 7.0. The high affinity of 4,4′‐DCB to PG is mainly a result of strong π–π interactions, as also confirmed by DFT calculations. The results reveal that PG sheets hold promise for the removal of persistent organic pollutants. We expect possible applications of this fast and mild plasma technique in the fabrication of nanomaterials and envisage their use in a variety of advanced chemical processes.     

Study of reactive ion etching of Si and SiO2 for CFxCl4−x gases

A parametric study of the etching of Si and SiO₂ by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF₄, CF₃Cl, CF₂Cl₂, and CFCl₃ (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO₂ as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF₂. The activation energy for the etching reaction of Si during CF₄ RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO₂ depended more strongly on the sheath voltage than on the F-to-Cl ratio.     

High‐Resolution Surface Chemical Analysis of a Trifunctional Pattern Made by Sequential Colloidal Shadowing

We present a new method for creating surface chemical patterns where three chemistries can be periodically arranged at alternate positions on a single substrate without the use of top‐down approaches. High‐resolution chemical imaging by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), with nanometer spatial resolution, is used to prove the success of the patterning and subsequent chemical modification steps. We use a combination of colloidal self‐assembly, plasma etching, self‐assembled monolayers (SAMs) and physical vapour deposition (PVD). The method utilizes a double colloid assembly process in which a first layer of close‐packed colloids is created, followed by plasma etching, coating with gold and deposition of a first SAM layer. A second particle layer is deposited on top of the first layer masking the interstitial spaces containing the first SAM. A second gold layer is deposited followed by a second SAM. After particle removal the surface consists of the pattern containing two different SAMs and a SiO₂ layer that can be readily functionalized with silanes. The possibility in the replacement of the two different thiols is investigated by X‐ray photoelectron spectroscopy (XPS) and it was found that no replacement is taking place. ToF‐SIMS imaging is used to show the periodicity of the chemical patterns by tracking unique fragment ions from the different surface regions. The patterning method is adaptable to create smaller or larger chemical patterns by appropriate choice of particle sizes. The patterns are useful for immobilizing biomolecules for cell studies or as multiplexed biosensors.     

Selective Growth of GaN on Slope Cone-shaped Patterned Sapphire Substrate

Cone-shaped patterned sapphire substrate was prepared by inductively coupled plasma etching and GaN nucleation layer was grown on it by metal-organic chemical vapor deposition.A selective growth of GaN nucleation layer was found on the slope of the cone-shaped patterned sapphire substrat,and the distribution morphology of GaN had significantly changed after it was recrystallized.GaN selective growth and redistribution were analyzed by investigating the distribution of crystallographic planes on the cone surface and the atom array of specific planes at atom level.     

Photolithographic surface micromachining of polydimethylsiloxane (PDMS)

A major technical hurdle in microfluidics is the difficulty in achieving high fidelity lithographic patterning on polydimethylsiloxane (PDMS). Here, we report a simple yet highly precise and repeatable PDMS surface micromachining method using direct photolithography followed by reactive ion etching (RIE). Our method to achieve surface patterning of PDMS applied an O(2) plasma treatment to PDMS to activate its surface to overcome the challenge of poor photoresist adhesion on PDMS for photolithography. Our photolithographic PDMS surface micromachining technique is compatible with conventional soft lithography techniques and other silicon-based surface and bulk micromachining methods. To illustrate the general application of our method, we demonstrated fabrication of large microfiltration membranes and free-standing beam structures in PDMS.     

Depth profiling of light elements in PAMBE‐grown GaN and helium‐implanted titanium with heavy ion time‐of‐flight elastic recoil detection

The heavy ion time‐of‐flight elastic recoil detection analysis (HI‐ERDA) technique was used to investigate the possibility of measuring near‐surface elemental depth profiles of light and mid‐Z elements in thin films of plasma‐assisted molecular beam epitaxy (PAMBE)‐grown GaN and helium‐implanted titanium. The great advantage of HI‐ERDA is the ability to measure mass‐separated elemental depth profiles simultaneously. However for some materials it is not certain whether HI‐ERDA can be used successfully because significant sputtering or other beam‐induced damage may occur. The damage to the surfaces by a 77 MeV iodine beam was assessed using RBS, AFM and profilometry. The results show that for thin PAMBE‐grown polycrystalline GaN films and for titanium that has been heavily implanted with helium a significant modification of the near‐surface region is caused by the probing heavy ion beam. For the PAMBE‐grown GaN films the most significant loss trend is observed for nitrogen. Surprisingly this was not accompanied by a change in surface topology. In contrast, an almost complete removal of the heavily helium‐implanted surface layer was measured for the titanium specimens. The investigation shows that reference measurements with additional techniques such as RBS, AFM and profilometry have to be performed to ascertain sample integrity before HI‐ERDA data can be used. Copyright © 2004 John Wiley & Sons, Ltd.     

Evaluation of the surface free energy of spin‐coated photodefinable epoxy

The surface free energy of crosslinked photodefinable epoxy (PDE) was evaluated from the advancing contact angles measured by the sessile drop method. Poly(tetrafluoroethylene) (PTFE) was used as a reference material in the evaluation of the surface free energies by various models. Pure water, diiodomethane, formamide, ethylene glycol, diethylene glycol, glycerol, 1‐bromonaphthalene, decane, and tetradecane were used as the probing liquids. The surface free energies for PDE and PTFE were calculated to be 43.6 and 21.2 mJ/m², respectively. The contact‐angle measurements indicated the isotropy of the PDE surface with respect to the surface free energy. The PDE coating was further characterized with scanning electron microscopy and atomic force microscopy. The PDE surface was treated chemically and by reactive ion etching (RIE) to determine their impact on the wettability and adhesion. The treatments resulted in decreased contact angles between the crosslinked PDE surface and water as the polarity of the surface increased from about 9% to 18 and 43% by the chemical and RIE treatments, respectively. On the contrary, the surface free energy of the treated PDEs, as calculated by the geometric mean model, did not change markedly (to 47.4 and 41.8 mJ/m² by the chemical and RIE treatments, respectively). Consequently, the contact angles of diiodomethane and the PDE solution on the treated surfaces did not decrease noticeably. The stud‐pull test showed improved adhesion strength for PDE that was left less crosslinked and, therefore, had residual affinity against the sequential PDE layer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2137–2149, 2002     

FTIR Analysis of Plasma Damage of Kapton

Recently, Kapton (polyimide) has been used in the reduction of dust particles in plasma etching chambers. However, it is found that there is a limit of lifetime for Kapton in trapping particles. Beyond this time limit, particle contamination becomes serious and even causes defect on wafers. In this study, two plasma etching recipes were used to test the particle/polymer trapping efficiency of Kapton. A Fourier Transform Infrared (FTIR) spectrometer was used to examine the functional groups change of the Kapton surface after plasma etching. The increase of IR absorption of CF_x (x = 2, 3) indicates the growth of fluorocarbon polymer on the Kapton surface. The Kapton surface was damaged as indicated by the change of C=O, -NH₂, and C - H IR intensities. IR Spectroscopic data show that Kapton has a very good particle/polymer reduction efficiency when using high-polymer recipe but not very efficient with oxygen-rich recipe. It has drawn our attention that when testing metal contamination of the processed wafers using chambers with Kapton coating, the concentration of aluminum was always high as compared to those without using Kapton. It can be ascribed to the plasma damage of Kapton, as supported by the surface chemical analysis with energy dispersion spectroscopy (EDS). Data collected from FTIR and EDS are correlated to interpret the mechanisms of plasma damage of Kapton.     

Compact plasma source for removal of hydrocarbons for surface analysis

A low–energy, constricted‐anode Anders‐type plasma source was built and tested for the chemical removal of adventitious carbon on surfaces. Oxygen plasma, generated in the source, extends to the sample surface through an aperture in the anode. This plasma reacts with surface hydrocarbons and removes them in less than a minute without influencing the intrinsic surface stoichiometry of nonoxidizing samples such as minerals, glasses, and metal oxides. Adventitious carbon removal is critical for accurate binding energy determination and quantitative measurements in XPS and AES, particularly in multicomponent materials. We measure the plasma to be composed primarily of O⁺ and O₂⁺, with minor H⁺, H₂⁺, and O⁺⁺ components. Ion energy distributions were measured for O⁺ and O⁺⁺ and show all emitted ions have energies less than 50 eV, confirming chemical desorption as the primary removal mechanism. The plasma source, easily built ‘in house’, is compact and can be mounted on a 2.75‐in flange for in situ specimen cleaning prior to surface analysis. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of Ar‐ and Ar/O2‐plasma‐treated amorphous and crystalline polymer surfaces revealed by ToF‐SIMS and principal component analysis

The effects of argon (Ar) and a mixture of Ar and oxgyen(Ar/O₂) plasmas on amorphous and semi‐crystalline poly(bisphenol A hexane ether) thin films were investigated by time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) and principal component analysis (PCA). PCA results of the ToF‐SIMS spectra indicate that an Ar/O₂ plasma produced less physical sputtering and had a higher chemical reactivity than did an Ar plasma, regardless of whether an amorphous or a crystalline surface was involved. However, the chemical differences between the Ar‐ and Ar/O₂‐plasma‐treated semi‐crystalline films were much smaller. The observed results can be explained by the higher resistance of the polymer crystalline regions to physical sputtering and chemical etching. Copyright © 2013 John Wiley & Sons, Ltd.     

Low temperature plasma for the preparation of crater walls for compositional depth profiling of thin inorganic multilayers

An indirect, compositional depth profiling of an inorganic multilayer system using a helium low temperature plasma (LTP) containing 0.2% (v/v) SF₆ was evaluated. A model multilayer system consisting of four 10 nm layers of silicon separated by four 50 nm layers of tungsten was plasma‐etched for (10, 20, 30) s at substrate temperatures of (50, 75, and 100) °C to obtain crater walls with exposed silicon layers that were then visualized using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) to determine plasma‐etching conditions that produced optimum depth resolutions. At a substrate temperature of 100 °C and an etch time of 10 s, the FWHM of the second, third, and fourth Si layers were (6.4, 10.9, and 12.5) nm, respectively, while the 1/e decay lengths were (2.5, 3.7, and 3.9) nm, matching those obtained from a SIMS depth profile. Though artifacts remain that contribute to degraded depth resolutions, a few experimental parameters have been identified that could be used to reduce their contributions. Further studies are needed, but as long as the artifacts can be controlled, plasma etching was found to be an effective method for preparing samples for compositional depth profiling of both organic and inorganic films, which could pave the way for an indirect depth profile analysis of inorganic–organic hybrid structures that have recently evolved into innovative next‐generation materials. Copyright © 2016 John Wiley & Sons, Ltd.     

A comparative study between inductively and capacitively coupled plasma deposited polystyrene films: chemical and morphological characterizations

Thin polystyrene films were deposited on stainless steel substrates by capacitively and inductively coupled radio frequency glow discharge plasma, in order to compare their chemical and morphological properties. The films were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐Ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), atomic force microscopy (AFM) and scanning electron microscope (SEM). Wettability properties were also determined by contact angle measurements. Ageing effect was studied by analysing films aged for 15 min and for 1 week. Results from both capacitively and inductively plasma polymerized polystyrene (pPS) films aged for 15 min showed that the chemical structure of the bulk, chemical composition of the surface (depth < 10 nm) and wettability properties were rather similar. Only their microstructures were very different: the pPS_capa film's microstructure showed homogeneous distribution of spherical particles of about 100 nm in diameter but the pPS_ind film's microstructure seemed to be mainly influenced by the surface of the metallic substrate: orientated ‘lamellae‐like layers’ of polymers were observed on each metallic grain. Ageing for 1 week in ambient air induced low oxygen uptake in the surface of both pPS films. The pPS_ind topmost surface (depth < 3 nm) was more oxidized than that of pPS_capa but no modification of the chemical structure of the bulk or of the morphology was noticed after ageing. Copyright © 2006 John Wiley & Sons, Ltd.     

Chemical‐surface modification of polymers using atmospheric pressure nonequilibrium plasmas and comparisons with vacuum plasmas

We demonstrate that stable microwave‐coupled atmospheric pressure nonequilibrium plasmas (APNEPs) can be formed under a wide variety of gas and flow‐rate conditions. Furthermore, these plasmas can be effectively used to remove surface contamination and chemically modify polymer surfaces. These chemical changes, generally oxidation and crosslinking, enhance the surface properties of the materials such as surface energy. Comparisons between vacuum plasma and atmospheric plasma treatment strongly indicate that much of the vacuum‐plasma literature is pertinent to APNEP, thereby providing assistance with understanding the nature of APNEP‐induced reactions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 95–109, 2002     

Removal of Tin from Extreme Ultraviolet Collector Optics by <Emphasis Type="Italic">In</Emphasis>-<Emphasis Type="Italic">Situ</Emphasis> Hydrogen Plasma Etching

Extreme ultraviolet (EUV) lithography produces 13.5 nm light by irradiating a droplet of molten Sn with a laser, creating a dense, hot laser-produced plasma and ionizing the Sn to the + 8 through + 12 states. An unwanted by-product is deposition of Sn debris on the collector optic, which focuses the EUV light emitting from the plasma. Consequently, collector reflectivity is degraded. Reflectivity restoration can be accomplished by means of Sn etching by hydrogen radicals, which can be produced by an H₂ plasma and etch the Sn as SnH₄. It has previously been shown that plasma cleaning can successfully create radicals and restore EUV reflectivity but that the Sn removal rate is not necessarily limited by the radical density. Additionally, while Sn etching by hydrogen radicals has been shown by multiple investigators, quantification of the mechanisms behind Sn removal has never been undertaken. This paper explores the processes behind Sn removal. Experiments and modeling show that, within the parameter space explored, the limiting factor in Sn etching is not radical flux or SnH₄ decomposition, but ion energy flux. Thus the removal is akin to reactive ion etching.     

Non-Steady-State Combined Process of Etching and Imidization of Polyamidoacid Film in Nonequilibrium Oxygen Plasma

The non-steady-state process of etching of a polyamidoacid film in an nonequilibrium oxygen low-pressure inductively coupled radiofrequency-discharge plasma was studied. It was shown that an unsteady imidization process develops in the bulk of the film simultaneously with occurrence of an unsteady film etching process. The time dependence of film etching rate at varying film thickness and incident ion energy was determined. The mechanism of the unsteady etching–imidization process of the polyamidoacid film in an oxygen plasma and the role of oxygen atoms and molecules in the process are discussed.     

Ultrathin Silicon-Compound Barrier Coatings for Polymeric Packaging Materials: An Industrial Perspective

Growing demands for increased shelf-life of food products and chemical inertia of the contact surfaces have stimulated development of polymers with improved high-barrier properties. Our objectives in this article are (1) to describe experimental results on Plasma-enhanced chemical vapor deposition (PECVD) and its importance to produce thin layers of inorganic glassy barrier materials for food, pharmaceutical, and organic display applications; (2) despite the thereby greatly enhanced quality of film or rigid packaging material, some residual coating defects result in less-than-perfect gas, moisture and aroma barriers: an innovative technique based on reactive ion etching (RIE) in oxygen plasma is also presented, along with a staining method, which render even sub-m coating defects visible. Data are shown for oxygen transmission rate on virgin and defective coatings, and the industrial context and applications are presented.