Substrate temperature effects on film chemistry in plasma depositions of organics. II. Polymerizable precursors

The influence of substrate temperature during plasma deposition on the chemistry of the organic films formed was examined. Plasma ionization of precursor gases that are polymerizable by conventional mechanisms was studied. Film chemistry was analyzed by x-ray photoelectron spectroscopy (XPS). Monomers that polymerize by a free radical mechanism [2-hydroxyethyl methacrylate (HEMA) and hexafluorobutadiene (HFB)] form more regular polymers (i.e. with less molecular rearrangement) by plasma deposition at low substrate temperatures than monomers that polymerize by ionic mechanisms [ethylene oxide (EO) and tetrahydrofuran (THF)]. In all cases, lowering the substrate temperature during deposition produces films with elemental composition virtually identical to that of the precursor gas. Comparison of high-resolution XPS spectra of the deposited films with those for model polymers suggests that functional groups in the monomers used to generate the plasma are incorporated to a greater extent at low substrate temperatures. The effect of plasma power on the degree of precursor structure retention obtained when reduced substrate temperatures are employed was also examined. Plasma deposition of HEMA at low substrate temperatures and low plasma power produces thin films which are, by core level XPS, indistinguishable from HEMA polymerized by conventional methods. EO and THF films coated at low substrate temperatures on glass, polyethylene, or polytetrafluoroethylene varied widely in surface chemistry due to differences in film uniformity. Film quality (uniformity) is enhanced for these low reactivity precursors by pretreating substrates with an argon plasma. © 1992 John Wiley & Sons, Inc.     

Molecular adsorption and the chemistry of plasma-deposited thin organic films: Deposition of oligomers of ethylene glycol

Weakly ionized, radio-frequency, glow-discharge plasmas formed from methyl ether or the vapors of a series of dimethyl oligo(ethylene glycol) precursors (general formula: H-(CH₂OCH₂)_n-H;n=1 to 4) were used to deposit organic thin films on polytetrafluoroethylene. X-ray photoelecton spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS) of the thin films were used to infer the importance of adsorption of molecular species from the plasma onto the surface of the growing, organic film during deposition. Films were prepared by plasma deposition of each precursor at similar deposition conditions (i.e., equal plasma power (W), precursor flow rate (F), and deposition duration), and at conditions such that the specific energy (energy/mass) of the discharge (assumed to be constrained byW/FM, whereM=molecular weight of the precursor) was constant. At constantW/FM conditions, two levels of plasma power (and, hence, twoFM levels) and three substrate temperatures were examined. By controlling the energy of the discharge (W/FM) and the substrate temperature, these experiments enabled the study of effects of the size and the vapor pressure of the precursor on the film chemistry. The atomic % of oxygen in the film surface, estimated by XPS, and the intensity of theC-O peak in the XPS C_ls spectra of the films, were used as indicators of the degree of incorporation of precursor moieties into the plasma-deposited films. Analysis of films by SIMS suggested that these two measures obtained from XPS were good indicators of the degree of retention in the deposited films of functional groups from the precursors. The XPS and SIMS data suggest that adsorption of intact precursor molecules or fragments of precursor molecules during deposition can have a significant effect on film chemistry. Plasma deposition of low vapor pressure precursors provides a convenient way of producing thin films with predictable chemistry and a high level of retention of functional groups from the precursor.     

Plasma polymerization and deposition of glycidyl methacrylate on Si(100) surface for adhesion improvement with polyimide

Thin polymer films were deposited on Si(100) surfaces by plasma polymerization of glycidyl methacrylate (GMA) under different glow discharge conditions. The FT‐IR, X‐ray photoelectron spectroscopy (XPS), and amine treatment results suggested that the epoxide functional groups of the deposited films had been preserved to various extents, depending on the plasma deposition conditions. The use of a low radio frequency power (～ 5 W) and a relatively high system pressure (100–400 Pa) readily resulted in the deposition of thin films having nearly the same composition of the epoxide functional groups as that of the GMA homopolymer. The plasma‐polymerized GMA (PP‐GMA) thin films deposited on the Ar plasma‐pretreated Si(100) surfaces were retained to a large extent after acetone extraction, suggesting the presence of covalent bonding between the PP‐GMA layer and the Si surface. Thermal imidization of the poly(amic acid) precursor of polyimide on the GMA plasma‐polymerized Si(100) surface resulted in a strongly adhered polyimide film. The adhesion results further suggested that the GMA polymer had been grafted on the Si(100) surface and the epoxide functional groups had undergone reactive interaction (curing) with the carboxylic and amine groups of the poly(amic acid) during thermal imidization. Copyright © 2001 John Wiley & Sons, Ltd.     

A ToF‐SIMS investigation of a buried polymer/polymer interface exposed by ultra‐low‐angle microtomy

The interfacial region of a model multilayer coating system on an aluminium substrate has been investigated by high‐resolution time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Employing ultra‐low‐angle microtomy (ULAM), the interface between a poly(vinylidene difluoride) (PVdF)‐based topcoat and a poly(urethane) (PU)‐based primer ‘buried’ >20 µm below the PVdF topcoat's air/coating surface was exposed. Imaging ToF‐SIMS and subsequent post‐processing extraction of mass spectra of the ULAM‐exposed interface region and of the PVdF topcoat and PU primer bulks indicates that the material composition of the polymer/polymer interface region is substantially different to that of the bulk PVdF and PU coatings. Analysis of the negative ion mass spectra obtained from the PVdF/PU interface reveals the presence of a methacrylate‐based component or additive at the interface region. Reviewing the topcoat and primer coating formulations reveals that the PVdF topcoat formulation contains methyl methacrylate (MMA)–ethyl acrylate (EA) acrylic co‐polymer components. Negative ion ToF‐SIMS analysis of an acrylic co‐polymer confirms that it is these components that are observed at the PVdF/PU interface. Post‐processing extraction of ToF‐SIMS images based on the major ions of the MMA–EA co‐polymers reveals that these components are observed in high concentration at the extremities of the PVdF coating, i.e. at the polymer/polymer interface, but are also observed to be distributed evenly throughout the bulk of the PVdF topcoat. These findings confirm that a fraction of the MMA–EA acrylic co‐polymers in the formulation segregate to the topcoat/primer interface where they enhance the adhesive properties exhibited by the PVdF topcoat towards the underlying PU primer substrate. Copyright © 2004 John Wiley & Sons, Ltd.     

Growth of organic n-conductors on thin polymer films for use in organic field effect transistors

Thin films of different polymers - poly(styrene) (PS), poly(methylmethacrylate) (PMMA), poly(vinylcarbazole) (PVCz), poly(vinylchloride) (PVC) and poly(vinylidene fluoride) (PVDF) - were deposited by spin-coating or by vapor deposition. On these polymers, thin films of (hexadecafluorophthalocyaninato)-oxovanadium (F₁₆PcVO) were prepared by physical vapor deposition. The growth of these films was monitored in situ by optical spectroscopy. The optical absorbance spectra were analyzed based on the coupling of transition dipoles to obtain information on the intermolecular arrangement of chromophores in the films. In all of these samples, the molecules are oriented with their molecular plane preferentially perpendicular to the substrate surface. This gives the desired overlap of the π-systems for electric conductance parallel to the substrate. Differences in the interactions were detected when deposition temperatures below or above the glass transition temperature of a given polymer were compared. The morphology of the polymer films and the deposited semiconductors were investigated by atomic force microscopy and scanning electron microscopy. The influence of the chosen substrate on the film structure is determined. The optical and electric properties of the films could thereby be influenced and the applicability of such films as active layers in organic thin film transistors is discussed.     

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper

Surface modification of poly(tetrafluoroethylene) films by plasma polymerization and deposition of glycidyl methacrylate (GMA) was carried out. The effects of glow‐discharge conditions on the chemical structure and composition of the deposited GMA polymer were analyzed by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. XPS and FTIR results revealed that the epoxide groups in the plasma‐polymerized GMA (pp‐GMA) layer had been preserved to various extents, depending on the plasma deposition conditions. The morphology of the modified PTFE surface was investigated by atomic force microscopy (AFM). The pp‐GMA film with well‐preserved epoxide groups was used as an adhesion promotion layer to enhance the adhesion of the electrolessly deposited copper on the PTFE film. The T‐peel adhesion test results showed that the adhesion strength between the electrolessly deposited copper and the pp‐GMA‐modified PTFE (pp‐GMA‐PTFE) film was much higher than that between the electrolessly deposited copper and the pristine or the Ar plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3498–3509, 2000     

Thermal conversion of poly(paraphenylene–vinylene) precursor films: XPS and ESR studies

The conversion of the precursor into poly(phenylene–vinylene) (PPV) was studied by means of photoelectron spectroscopy (XPS) and electron spin resonance (ESR) on precursor films synthesized from the polymerization of pxylene-tetrahydrophenium halides. The sulfonium precursor containing chlorine or bromine was thermally converted to PPV and analyzed in situ using the spectrometers. It was found by XPS analysis that both halide precursors were thermally converted into polymer in a range of 190–250°C but traces of bromine were still present at >300 °C in the precursor containing Br. Furthermore, a small amount of oxygen in a ketone structure was also present in fully converted films. The ESR results corroborated the XPS experiments, showing a progressive disappearance of the radical distribution related to sulfur sites in a comparable temperature range. A discussion of the conversion process is given in terms of the modification of the core level spectra from XPS and the g distributions from ESR experiments. © 1997 John Wiley & Sons, Ltd.     

Surface characterization of the SiOx films prepared by a remote atmospheric pressure plasma jet

The deposition rate and surface properties of SiO_x films were prepared and investigated using remote atmospheric pressure plasma (APP) jet. The APP, generated with low frequency power at 16 kHz, was fed with tetraethoxysilane (TEOS)/air gas mixture. After deposition, the SiO_x films were analyzed for chemical characteristics, elemental composition, surface morphology, and hardness. It was found that the deposition substrate temperature is the key factor to affect the deposition rate of remote APP chemical vapor deposition process. Fourier transform infrared (FTIR) spectra indicated that APP deposited SiO_x films are an inorganic feature. XPS examination revealed that the SiO_x films contained approximately 30% silicon, 58% oxygen and 12% carbon. Atomic forced microscopy (AFM) analysis results indicated a smooth surface of SiO_x films in deposition under higher substrate temperature. Also, pencil hardness tests indicated that the hardness of APP deposited SiO_x films was greatly improved with increasing substrate temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

Plasma-enhanced deposition of diamond-like carbon films on high temperature tolerant polymers

The feasibility of depositing carbon films with a diamond-like structure on high temperature polymers, using established plasma-enhanced chemical vapor deposition techniques, is explored. Potential uses for such a film will depend upon the adhesion of the film to the substrate, the properties of the deposited film, and the effect of the deposition process on the bulk properties of the polymer substrate. Amorphous carbon (diamond-like carbon) coatings with thicknesses ranging from 2 to 18 μm were deposited on polyimide substrates at temperatures below 420°C. Extended exposure to the plasma processing conditions caused no visible damage but halved the room-temperature tensile strength of the polymer films. Diamond-like carbon, graphitic carbon, and a precursor to the diamond-like carbon structure, attributed to an aromatic carbon ring structure, were observed. The optical transparency of the coated polymer film was attenuated uniformly across the spectral range, 2.5-22 μm. Static oxidation and limited thermal cycling of the coated polymer produced no widespread delamination of the coating from the substrate: neither the deposited film nor the coated regions of the polymer showed any effect when oxidized at 370°C, for 450 h. © 1994 John Wiley & Sons, Inc.     

Sacrificial adhesion promotion layers for copper metallization of device structures

The adhesion of copper films to adjacent device layers including TiN, Ta, and TaN diffusion barriers is a crucial reliability issue for integrated circuits. We report that ultrathin layers of poly(acrylic acid) (PAA) prepared on barrier surfaces or on the native oxide of Si wafers dramatically increase the interfacial adhesion of Cu films deposited by the H2 assisted reduction of bis(2,2,7-trimethyloctane-3,5-dionato)copper in supercritical carbon dioxide. Similar improvements were achieved on Si wafers using a simple vapor phase exposure of the substrate to acrylic acid prior to metallization. The deposited films and the substrate/Cu interfaces were analyzed by X-ray photoelectron spectroscopy (XPS), electron microscopy, atomic force microscopy, and variable-angle spectroscopic ellipsometry. No trace of the adhesion layer was detected at the interface, indicating it was sacrificial at the deposition conditions used. Moreover, the presence and subsequent decomposition of the PAA layer during deposition substantially reduced or eliminated metal oxides at the substrate interface. For depositions on PAA-treated Si wafers, copper was present primarily as Cu0 at the interface and Si was present only as Si0. On PAA-treated Ta substrates, XPS analysis indicated Ta was present primarily as Ta0 at the metallized interface whereas Ta2O5 dominated the interface of samples prepared without the adhesion layers. The technique can be extended to patterned substrates using adsorption of acrylic acid or thermal/UV polymerization of acrylic acid.     

Surface structures of fluoropolymer,polyolefin and polyester films after modification by graft polymerization

Pristine and argon plasma pretreated polytetrafluoroethylene (PTFE), polystyrene (PS), high-density polyethylene (HDPE) and poly(ethylene terrephthalate) (PET) films have been subjected to near-UV light-induced graft polymerization with water-soluble acrylamide (AAm), the sodium salt of styrene sulfonic acid (NaSS), acrylic acid (AAc) and N,N-dimethylaminoethylmethylacrylate (DMAEMA) monomers. The structure and composition at the substrate surface with grafted polymer were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). In most cases, the density of surface grafting is enhanced by plasma pretreatment. For each polymer substrate with a substantial amount of grafting, the hydrophilic graft penetrates or becomes partially submerged beneath a thin surface layer of dense substrate chains. This stratified microstructure is consistent with the static secondary ion mass spectroscopy (SIMS) and Ar⁺ beam depth profiling results. The two latter techniques also suggest that when the grafted polymer has a bulky substituent, there is less efficient penetration of the grafted polymer below the surface.     

Plasma deposition and surface characterization of oligoglyme, dioxane, and crown ether nonfouling films

Plasma-deposited PEG-like films are emerging as promising materials for preventing protein and bacterial attachment to surfaces. To date, there has not been a detailed surface analysis to examine the chemistry and molecular structure of these films as a function of both precursor size and structure. In this paper, we describe radio-frequency plasma deposition of a series of short-chain oligoglymes, dioxane, and crown ethers onto glass cover slips to create poly(ethylene glycol)-like coatings. The resultant films were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), dynamic contact angle goniometry, and radiolabeled fibrinogen adsorption. Detailed analysis of the high-mass (120-300 m/z) TOF-SIMS oligoglyme film spectra revealed six classes of significant fragments. Two new models are proposed to describe how these fragments could be formed by distinct film-building processes: incorporation of intact and fragmented precursor molecules. The models also provide for the incorporation of hydrocarbon--a species that is not present in the precursors but is evidenced in XPS C(1s) spectra of these films. Two additional models describe the effects of incorporating intact and fragmented cyclic precursors.     

Influence of shape and surface properties of microstructured reaction areas on the deposition of silica

Differently shaped reaction areas for silica deposition were created by photochemical grafting of hydrophobic poly(acrylic acid 2-ethyl-hexylester) as barrier and a hydrophilic polymer employing a mask having hexagons, pentagons, squares and stripes. Poly(ethylene glycol), poly(acrylic acid), branched and linear poly(ethylene imine) and linear poly(methylpropylene imine) have been applied as hydrophilic polymer in the reaction area. These patterned films have been used in silica mineralization experiments by dipping them into a silica precursor solution. Investigations of the polymer films and silica depositions have been done by contact angle measurements, ellipsometry and scanning electron microscopy (SEM). Silica deposition occurs only in the hydrophilically coated areas, resulting in regular arrays of lens-like silica particles. There are only minor differences due to the shape of the reaction area. The influence of the different hydrophilic polymers can be explained by their wetting behaviour.     

A Comparative Study of Properties of Acrylic Based Water-Borne Polymers Using Various Surfactants for Adhesive Applications

Emulsion polymerization of styrene/vinyl acetate/methyl methacrylate with butyl acrylate, acrylic acid and acrylamide is investigated using conventional and polymerizable surfactants. The effect of different surfactants on the water resistance, adhesion and surface properties of the polymer films was studied. The performance of films obtained from latexes using conventional surfactants is compared with that of latexes using polymerizable surfactants. The study showed that polymerizable surfactants are bound to the polymer backbone in such a way that their migration to film surfaces during drying is inhibited which helps in achieving better water resistivity with good adhesive performance.     

Multitechnique characterization of thin films of immiscible polymer systems: PS–b‐PMMA diblock copolymers and PS–PMMA symmetric blends

Immiscible polymer systems are known to form various kinds of phase‐separated structures capable of producing self‐assembled patterns at the surface. In this study, different surface characterization methods were utilized to study the surface morphology and composition produced after annealing thin polymer films. Two different SIMS techniques—static time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and dynamic nano‐SIMS—were used, complemented by x‐ray photoelectron spectrometry (XPS) and atomic force microscopy (AFM). Thin films (spin‐coated onto silicon wafers) of polystyrene (PS)–poly(methyl methacrylate) (PMMA) symmetric blends and diblock copolymers of similar molecular weight were investigated. Surface enrichment by PS was found on all as‐cast samples. The samples were annealed at 160 °C for different time periods, after which the blend and the copolymer films exhibited opposite behaviour as seen by ToF‐SIMS and XPS. The annealed blend surface presented an increase in the PMMA concentration whereas that of copolymers showed a decrease in PMMA concentration compared with the as‐cast sample. For blends, the nano‐SIMS as well as AFM images revealed the formation of phase‐separated domains at the surface. The composition information obtained from ToF‐SIMS and XPS, as well as the surface mapping by nano‐SIMS and AFM, allowed us to conclude that PS formed phase separated droplet‐like domains on a thin PMMA matrix on annealing. The three‐dimensional nano‐SIMS images showed that the PS droplets were supported inside a rim of PMMA and that these droplets continued from the surface like columnar rods into the film until the substrate interface. In the case of annealed copolymer samples, the AFM images revealed topographical features resembling droplet‐like domains on the surface but there was no phase difference between the domains and the matrix. In the case of copolymers, owing to the covalent bonding between the blocks, complete phase separation was not possible. The three‐dimensional nano‐SIMS images showed domain structures in the form of striations inside the film, which were not continuous until the substrate interface. Information from the different techniques was required to gain an accurate view of the surface composition and topographical changes that have occurred under the annealing conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Deposition of Gallium Nitride Thin Films by MOCVD in Microwave Plasma

The deposition of GaN thin films in a nitrogen–hydrogen microwave plasma using Ga(CH ₃ ) ₃ as a gallium precursor was investigated. The deposit was identified as stoichiometric GaN by XPS and XRD. The substrate was dielectrically heated in the microwave discharge and the substrate temperature was lower than that in usual thermal MOCVD. The NH radicals, which were the primary N-atoms precursors, and fragments of Ga(CH ₃ ) ₃ were identified in the plasma by OES. The NH radical formation and the decomposition of Ga(CH ₃ ) ₃ in the plasma may be one of the reasons for the lower deposition temperature of GaN. The position dependence of the substrate temperature showed similar tendency as the position dependence of the electron temperature. The plasma state contributes to the deposition of GaN thin films. The deposited GaN exhibited a wide optical band gap of 3.4eV. Material highly oriented along the c axis was detected in the deposit, and a PL spectrum which has the band head at about 450 mm was obtained.     

Secondary ion mass spectrometry and X-ray photoelectron spectroscopy investigation on chemical vapor deposited CeO(2-)ZrO(2)-TiO(2) thin films

Mixed CeO(2)-ZrO(2) systems have attracted widespread interest for their use in three-way catalyst (TWC) technology for automotive exhaust conversion to non-toxic products. In this work, CeO(2)-ZrO(2) thin films were deposited, via chemical vapor deposition, in order to obtain nanoscale materials with a high surface-to-volume ratio, with precise control of system properties. The addition of TiO(2) as buffer layer was also investigated. Cordierite was chosen as substrate, being the usual refractory material for catalytic mufflers. The multilayers were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). In particular, the combination of SIMS and XPS allowed us to investigate both surface and in-depth chemical composition, studying also film-intermixing phenomena induced by annealing processes.     

Synthesis,characterization, and thermal properties of novel silicon 1,1,3,3-tetramethylguanidinate derivatives and use as single-source chemical vapor deposition precursors

A series of chemical vapor deposition (CVD) precursors have been synthesized by a single-step reaction of 1,1,3,3-tetramethylguanidine and a variety of silicon chlorides. The structures of the 1,1,3,3-tetramethylguanidinate-based compounds were verified by ¹H NMR, ¹³C NMR, XPS, EI-MS, and elemental analysis. The thermal stability, transport behavior, and vapor pressures of these compounds were evaluated by simultaneous thermal analyses (STA). These compounds are highly stable and those in liquid form are very volatile. Silicon carbonitride (SiCN) thin films were prepared by using bis (tetramethylguanidine)-dimethyl-silane as the precursor in helicon wave plasma chemical vapor deposition (HWP-CVD). The properties of the films were investigated by SEM, AFM, and XPS. The results showed that the films have good uniformities, low friction coefficient, and high hardness, enabling the films for fabrication of semiconductor devices.     

Early steps in layer-by-layer construction of polyelectrolyte films: the transition from surface/polymer to polymer/polymer determining interactions

The layer-by-layer deposition of two polyelectrolytes, quaternized poly(dimethylaminoethyl methacrylate chloride) (MADQUAT) and poly(acrylic acid) (PAA) on a silica substrate was investigated using optical reflectometry, as a function of pH (pH 4, 5.5 and 9), ionic strength (10(-3) to 10(-1) M) and type of salt. Attention was given to the successive deposited weights and to the corresponding deposited charge densities within the ten first deposited layers. Results show a change of growth regime between an early stage where the substrate had a dominating influence in the build-up and a second stage where the polymer uptake was ruled essentially by polymer-polymer interactions. The pH was seen to influence the growth via the charge densities of silica (first stage) and PAA (first and second stages). The increase of NaCl concentration induced an increase of the film weight between 10(-3) and 10(-2) M, but the trend was more sophisticated between 10(-2) and 10(-1) M where the polymer uptake increased in the first stage of the growth and decreased in subsequent layers. The film weight increased in accordance with the rank of ions in the Hofmeister series. AFM images revealed a heterogeneous film morphology with bumps and valleys, which was explained by a growth mechanism made of the successive formation and growth of polymer complexes.     

A Three-Dimensional Two-Phase Model for Thermal Plasma Chemical Vapor Deposition with Liquid Feedstock Injection

In this paper, a comprehensive model for thermal plasma chemical vapor deposition (TPCVD) with liquid feedstock injection is documented. The gas flow is assumed to be steady, of a single temperature. Radiation and charged species contributions are excluded, but extensive homogeneous and heterogeneous chemistry is included. The liquid phase is traced by considering individual droplets. Discussion on the model's application to diamond production from acetone in a hydrogen–argon plasma is included. The major conclusions are: (1) Liquid injection possesses a capability to deliver the hydrocarbon precursor directly onto the deposition target. (2) For the case of complete evaporation of the droplet before reaching the substrate, the deposition rate is similar to that obtained with gaseous precursors. (3) The computational results compare well with experimental data. The modeling results can be used to optimize the injection parameters with regard to the deposition rate.