Adhesion Between Plasma-Treated Polypropylene Films and Thin Aluminum Films

Polypropylene (PP) film was treated with radio-frequency-induced oxygen plasma, followed by the vacuum deposition of aluminum (Al) thin film, and the peel strength of the Al deposited PP film (Al/PP) was examined. The peel strength of plasma-treated PP film varied widely in the range of 6.7 to 157 N/m depending upon the plasma treatment conditions, whereas that of the untreated PP was 5.2 N/m. The peel strength was minimized at oxygen pressure near 13.3 Pa (0.1 Torr), and decreased with increasing discharge power. The peel strength rapidly increased at the initial stage of plasma treatment (∼ several seconds), decreased at the second stage, and slightly increased again at the third stage. A good agreement was found between the peel strength of Al/PP and the amounts of oxygen introduced onto the PP surface at the initial stage. A short-time treatment was very effective to improve the adhesion of Al/PP. At the end of the second stage, a large amount of carbon was detected by XPS on the Al layer of the peeled interface of Al/PP, which gave a minimum peel strength. Cohesive failure of PP film might have occurred. SEM photograph showed that PP surface was etched by oxygen plasma at the thrid stage. These peel behaviors of Al/PP were explained by the chemical and physical changes of the PP surface caused by oxygen plasma treatment: (1) introduction of O-functional groups onto the PP surface at the initial stage, (2) formation of weak booundary layers resulting from the partial scission of PP molecules at the second stage, and (3) plasma etching of the PP surface at the third stage.     

Adhesion Properties and Structure of Ion-Beam Modified Polyimide Films

Polyimide (PI) surface modification was carried out by an ion beam treatment to improve the adhesion between the polyimide film and copper. The PI film surface was treated with an ion-beam source at ion doses ranging from 1.96 × 10¹³ to 2.38 × 10¹³ ions/cm² using a mixture of nitrogen (N₂) and hydrogen (H₂). Contact angle measurement, atomic force microscopy and X-ray photoelectron spectroscopy, respectively revealed an increase in the surface roughness, a decrease in contact angle, and the formation of oxygen complexes and functional groups on the treated PI surfaces. Adhesion between the copper and PI film treated with the beam was superior to that of the untreated PI film. The 90° peel test revealed the highest peel strength of 7.8 N/cm.     

Effects of titania content and plasma treatment on the interfacial adhesion mechanism of nano titania-hybridized polyimide and copper system

Nano-titania (TiO₂) incorporated into polyimide (PI) matrix can significantly enhance the adhesion strength for PI/TiO₂ hybrid film and copper system. Surface modifications by various plasma treatments (Ar, Ar/N₂ and Ar/O₂) were also applied in this study to improve the adhesion strength. The Ar/N₂ plasma treatment is regarded as the more effective way in promoting the adhesion strength. The maximum adhesion value of 9.53 N/cm was obtained for the PI/TiO₂-1 wt% hybrid film with Ar/N₂ plasma treatment. It is enhanced about 10 times as large as pristine PI. Furthermore, by Ar/O₂ plasma treatment, a weak boundary of copper oxide was formed at the interlayer between PI/TiO₂ hybrid film and copper which decreases the adhesion strength. The effects of plasma treatment and content of nanosized TiO₂ on the adhesion strength between PI/TiO₂ hybrid film and copper system were studied. Atomic force microscope and contact angle analyses were used to measure the changes in surface morphology and surface energy as a result of plasma treatment. Besides, the interfacial states of peeled-off polymer side and copper side were investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Based on the result of XPS spectra, the peeled-off failure mode between PI/TiO₂ hybrid film and copper was proposed in this study.     

Tantalum and chromium adhesion to polyimide. Part 2. Peel and locus of failure analyses

Ta and Cr adhesion to 3,3'-4,4'-biphenyl tetracarboxylic acid dianhydride-p-phenylenediamine derived (BPDA-PDA) polyimide (PI) surfaces has been studied before treatment, and after CF₄ reactive ion etching (RIE), and Ar sputtering. The initial peel adhesion results for both metals on the BPDA-PDA surfaces are comparable and show increased peel adhesion as a function of the surface treatment in the following order: virgin (no treatment) < Ar sputter < CF₄ RIE ~ CF₄ RIE followed by Ar sputter. The surface roughness effect on metal/PI adhesion has also been investigated. The data suggest that the surface roughness does not primarily affect peel adhesion. In this case, it is the removal of the weak boundary layer and the cracking of the residual PI on the metal peel interface surface during the peeling process which cause the increase in the peel strength. It is also proposed that the changes observed in the peel strength as a function of the surface treatment are due to differences in the fracture toughness of the modified PI layers rather than differences in the surface roughness.     

Surface modification of poly(tetrafluoroethylene) film by chemical etching,plasma, and ion beam treatments

Chemical etching, plasma, and ion beam treatments were used to modify the surface of Polytetrafluoroethylene (PTFE). Each surface treatment method developed different surface characteristics. In addition to morphological observation, contact angle, atomic chemical composition, and adhesion strength were measured after treatment with various methods. The different adhesion strengths were explained based on the morphology and atomic chemical composition of the treated PTFE surfaces. The chemical etching showed substantial defluorination, and the adhesion strength was fairly high. The argon plasma treatment introduced very large amounts of oxygen into the surface, and the surface was very smooth with a crater‐like structure. Ion beam treatment induced a form of spires whose dimensions were of several micrometers, depending on the ion dose, whereas the oxygen plasma‐treated samples showed short spires with spherical particles on the top. The spire‐like surface morphology and increased surface area during bonding by ion beam treatment appear to be the reason for a higher adhesion strength than that of the oxygen plasma‐treated PTFE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1913–1920, 2000     

Adhesion enhancement of polyimide on copper by Ar ion beam etching of copper

Ar ion beam etching (IBE) can be used to roughen a Cu surface and thus improve the adhesion of subsequently spin-coated polyimide (PI) films. During Ar IBE, the surface morphology of sputter-deposited Cu changes from round bumps to a rough cone structure. The ultimate tensile strength (UTS) of the PI/Cu interface is increased for certain specific beam conditions. Under optimal conditions, the UTS of the etched PI/Cu interface (6.2 MPa) is twice that of the unetched PI/Cu interface (3.1 MPa). Cu is detected in the deposited PI by Rutherford backscattering spectrometry (RBS). The amount of Cu at the top surface of the 2.5 μm thick PI film is 0.1 at. %; this is determined by RBS and XPS. While the Cu is dissolved by polyamic acid and diffuses into the PI, an oxygen-rich region is formed in the Cu. The oxygen-rich region in Cu grows from 50 A (approximately Cu₂O) before PI deposition to more than 2000 A (where the oxygen concentration is about 5 at. %) after PI deposition. The oxygen source is not the PI itself but either dissociated oxygen from the water vapor in the PI imidization process or a product of the chemical reaction between Cu and polyamic acid.     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

Superficial modification in recycled PET by plasma etching for food packaging

An oxygen plasma treatment has been used to improve the adhesion of amorphous hydrogenated carbon (a‐C:H) films onto surfaces of recycled poly(ethylene terephthalate) (PET). Modifications produced by the oxygen plasma on the PET surface in chemical bonds and morphology were investigated by X‐ray photoelectron spectroscopy and atomic force microscopy, respectively. Contact angle measurements were used to study the changes in the surface wettability. Adhesion of the a‐C:H film onto the PET surface was investigated by the tape test method. It was observed that the improvement in film adhesion is in good correlation with the increase in surface roughness, due to plasma etching, and with the appearance of oxygen‐related functional groups at the surface. The results of this study indicate that a‐C:H‐coated recycled PET can be used in food packaging. The a‐C:H film could be used as a functional barrier to reduce or prevent migration of contaminants from the polymer to the package content. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface modification of polyimide by combining swelling and TiO2 photocatalytic treatments for adhesion improvement of electroless Cu

In order to enhance the adhesion strength between the PI film and the electroless copper film, a combination of swelling and TiO₂ photocatalytic treatments was used to modify polyimide (PI) film. The effects of the swelling solution composition and TiO₂ photocatalytic condition on the surface performance were investigated. After the optimal swelling and photocatalytic treatment, the surface contact angle of the PI film decreased from 85 to 28.7°, and the surface average roughness of the PI film only increased from 1.3 to 13.6?nm, indicating no obvious change for the surface topography of PI film after the photocatalytic treatment. However, the adhesion strength between electroless copper film and the PI film reached to 0.6?KN·m^?1. The FT-IR spectra and XPS analyses indicated that –COOH group was formed on the PI surface after the treatment, and the surface hydrophilicity was improved, which improved the adhesion strength between the PI film and the electroless copper film.     

Study on brown oxidation process with imidazole group,mercapto group and heterocyclic compounds in printed circuit board industry

The adhesion strength of the interface between copper foil and resin is an important technological parameter for applications in microelectronics. In this study, a new brown oxidation solution of copper foil, including the recipe composition and reliability tests, was fully discussed. We provided an overview of brown oxidation process used in the semi-flexible printed circuit boards production industry by investigating the brown oxide film. The morphology of the copper oxide film was changed from lamellar structure to honeycomb structure with the increasing of oxidation time. The peel adhesion strength of the Cu/polyimide laminates was increased from about 2–16 N/cm by altering the immersion time and the concentration of inhibitors in brown oxidation solution. Scanning electron microscopy, peel tests and X-ray diffraction indicated that the higher adhesion strength was resulted from the rougher surface and the proper etching depth of copper foil, which was caused by chemical reactions on the interface surface of copper foil.     

Peel strength improvement of silicone rubber film by plasma pretreatment followed by graft copolymerization

Here we discuss the improvement in the peel strength of silicone rubber film by O₂ plasma pretreatment followed by grafting with hydrophilic monomers: acrylamide (AAm) and acrylic acid (AA). The peroxides concentration after O₂ plasma treatment was determined by the 1,1-diphenyl-2-picrylhydrazyl (DPPH) method. ESCA analysis was carried out to confirm the existence of AAm. The peroxides concentration and hence the peel strength increased with increasing plasma treatment power and time, reached a maximum value, and then decreased with further increasing plasma treatment power and time. Peel strength of the silicone film with 3M-600 tape was observed to increase with grafting time; however, it was found to decrease with overgrafting. The maximum peel strength of 384.4 g/cm was found for the 20 W, 10 min plasma treated, AAm grafted film with maximum peroxides concentration of 4.86 x 10^-9 mol/cm² and also with maximum nitrogen-to-carbon ratio (N/C) of 0.247. Hydrolysis experiments show that -NH₂ provides higher contribution to adhesion than -COOH does and the grafting degree of AA is lower than that of AAm. The relationship between the degree of grafting and peel strength can be well explained by the mechanical interlocking theory of adhesion.     

Role of polymer chain end groups in plasma modification for surface metallization of polymeric materials

How to improve adhesion between poly(oxybenzoate‐co‐oxynaphthoate) (Vecstar OC and FA films) and copper metal by Ar, O₂, N₂ and NH₃ plasma modification was investigated. The mechanism of adhesion improvement is discussed from the viewpoint of chemical and physical interactions at the interface between the Vecstar film and copper metal layer. The adhesion between Vecstar OC film and copper metal was improved by chemical rather than physical interactions. Polymer chain end groups that occur at Vecstar OC film surfaces contribute effectively to adhesion. This improvement in adhesion is due to interactions between copper metal and O?C groups formed by plasma modification. Aggregation of the O?C groups to the copper metal/Vecstar OC film interface is a key factor for good adhesion. From this aspect, heat treatment of plasma‐modified Vecstar OC films on glass plates is effective in the aggregation, and the peel strength for the copper metal/Vecstar OC film system reached 1.21 N (5 mm)^?1. Copyright © 2009 Society of Chemical Industry     

A study of the environmentally friendly polycarbonate surface etching system containing H2SO4–MnO2 colloid

In this paper, an environmentally friendly etching system containing H₂SO₄–MnO₂ colloid was used to investigate surface etching for polycarbonate (PC). The effects of swelling condition, H₂SO₄ concentrations and etching times on surface topography and surface roughness were studied. With the etching treatment, the surface average roughness (R _a) of PC substrates increased from 3 to 76?nm and the adhesion strength between the electroless copper and PC substrate reached 1.08 KN/m. Surface chemistry of PC substrates was investigated by the contact angle measurement and X-ray photoelectron spectroscopy spectra (XPS). After the etching treatment, PC surface became hydrophilic and the contact angle decreased from 95.2 to 39.6^o. XPS analyses indicate that hydroxyl and carboxyl groups are formed on the PC surface as a result of the etching treatment, which improve the adhesion strength between PC substrate and electroless copper film.     

Surface modification of nylon 6 films treated with an He/O2 atmospheric pressure plasma jet

To investigate the effect of the gas composition of the plasma treatment on the surface modification of an atmospheric pressure plasma jet (APPJ), nylon 6 films were treated with APPJ with pure helium (He), He + 1% oxygen (O₂), and He + 2% O₂, respectively. Atomic force microscopy showed increased surface roughness, whereas X‐ray photoelectron spectroscopy revealed increased oxygen contents after the plasma treatments. The plasma‐treated samples had lower water contact angles and higher T‐peel strengths than the control. The addition of a small amount of O₂ to the He plasma increased the effectiveness of the plasma treatment in the polymer surface modification in terms of surface roughness, surface oxygen content, etching rate, water contact angle, and bonding strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Studies on metal/benzocyclobutene (BCB) interface and adhesion

Interfacial characteristics such as chemical reaction, metal diffusion, and morphology were investigated for Cu/BCB, Cr/BCB and Ti/BCB structures. Using Auger and XPS depth profiling, the formation of titanium carbide and chromium oxide was confirmed at the metal/BCB interface. Annealing at 250°C for extended periods resulted in the diffusion of Cu, Cr and Ti into the BCB and subsequent formation of Cu-Si, CrSi₂ and Ti-Si compound precipitates. The reaction is a thermal diffusion controlled process which is dependent on time and temperature. Ar sputtering treatment of BCB film before metallization was found to roughen the surface, resulting in metal spikes which penetrate into the roughened BCB film. However, the peel strength of metals on BCB was only about 177 g cm^_1presumably due to the brittleness of the BCB film. The etch rates of the BCB film in a reactive ion etcher (RIE) and a plasma etcher were measured using Ar, O₂, O₂ + CF₄, and O₂ + SF₆ gas mixtures. Faster etch rates were obtained when CF₄ and SF₆ were added to oxygen, since the presence of atomic fluorine enhances the etch rate of organics, while also etching Si and SiO₂ formed by exposure of Si-containing BCB film to oxygen gas. Surface compositional changes on the BCB film were observed by XPS after plasma modification. Pure O₂ and O₂ + CF₄ plasmas oxidized the carbo-siloxane linkage (C_—Si_—O) of the BCB, resulting in the formation of SiO₂ on the surface. The O₂ + SF₆ plasma, however, did not produce the surface SiO₂, because of its faster Si and SiO₂ etch rates.     

Changes in the adhesion strength between copper thin films and polyimide substrates after heat treatment

The adhesion strength between a copper (Cu) thin film and a polyimide [pyromellitic dianhydride-oxydianiline (PMDA-ODA)] substrate is reduced by heat treatment at 150°C in air. In this work, we determined the changes in adhesion strength between Cu films and polyimide substrates using Auger electron spectroscopy (AES), attenuated total reflection Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The analysis showed that the weak boundary layer (WBL) shifted towards the Cu interface as the heat treatment time was increased. To confirm this shift, we looked at two other polyimide substrates: biphenyl dianhydride-p-phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). Comparing the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but very low for the Cu/BPDA-PDA laminate. One of the possible reasons for this behavior could be that the ether moiety between the two benzene rings in ODA is related to the adhesion between a Cu film and an 0₂-plasma-treated polyimide (PI) substrate. The relationship between the adhesion strength and chemical bonding states is also discussed. We conclude that a Cu thin film sputtered onto a PI substrate is apt to peel at the oxidized interface, due to the heat treatment.     

An XPS study of argon ion beam and oxygen RIE modified BPDA-PDA polyimide as related to adhesion

Modification of polymer surfaces by changing the chemical structure, surface energy, and bonding characteristics has considerable technological importance in the area of adhesion. Reactive ion etching (RIE) and ion beam (IB) bombardment were employed to modify the surfaces of fully imidized 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride-p-diaminophenyl (BPDA-PDA)-based polyimide (PI) films. These modification techniques affect only a shallow surface region, approximately 10-20 nm, and the bulk properties of the polymer are unaffected. The angle-resolved X-ray photoelectron spectroscopy (XPS) technique was used to characterize the PI surfaces modified by argon IB bombardment or oxygen RIE treatment. On the argon ion-bombarded surfaces, the XPS spectra indicate that the carbonyl and imide groups are decreased. Oxygen RIE treatment resulted in an increase in the atomic concentration of oxygen. To understand the surface aging effect, the freshly modified PI surfaces were exposed to laboratory air for 1 and 2 days. The changes in composition as a function of the depth of the modified surface region right after treatment and after aging were determined by the angle-resolved XPS technique (ARXPS). Contact angle measurements were used to determine the polar and dispersion components, the sum of which is the surface free energy. The polar component of the surface free energy shows the greatest change, with an increase of 8.0-9.4 times for both the oxygen RIE and ion beam treatments as compared with the as-cured PI surface. Aging of these modified surfaces resulted in a decrease of surface free energy as compared with the just-modified surfaces. In the case of oxygen RIE treatment, the dispersion component of the surface free energy showed little or no change from the as-cured sample. Adhesion of chromium/copper/chromium (Cr/Cu/Cr) films on PI was determined by peel strength measurements. Significant increases in peel strength, by a factor of 10-80, were shown for the modified surfaces. A good correlation between the peel strength and the experimentally determined polar component of surface energy was shown.     

Improvement of adhesion of PET fibers to rubber by argon-oxygen plasma treatment

Polyethylene terephthalate fibers cords were modified with argon, oxygen, and successive argon/oxygen cold plasmas as a function of treatment time. Plasma treated cords were coated with resorcinol formaldehyde latex, then tested as rubber reinforcing materials. The peel strength was discussed with respect to the polar component of the surface energy and the etching of the fibers. An increased adhesion of ∼ 280% was obtained with 30 min argon plasma followed by 30 min oxygen plasma, at 75 W power and 40 Pa pressure without altering the traction strength of the fibers cords. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2321–2330, 1998     

Investigation on the etching of thick diamond film and etching as a pretreatment for mechanical polishing

Etching with oxygen plasma produced by DC glow discharge was investigated as a potential technique for etching of diamond films and as a pretreatment technique for mechanical polishing of thick diamond films. The influence of DC power and gas pressure to etched morphology and etching rate were studied using scanning electron microscopy and electronic micro-balance, respectively. The electron temperature and plasma density were measured by Langmuir single probe to explicate the influence mechanism of etching parameters according to an etching model. The effect of etching on mechanical polishing was studied through surface roughness measuring instrument and Raman spectrometer.It was found that at a constant gas pressure the rise of DC power would result in the increase of deepening etch pits overspreading from the protuberant facet to the boundary of diamond crystallites with rising etching rate. And the same tendency was engendered by reducing gas pressure when the DC power remained. The numerous etch pits can be ascribed to etching with a higher rate of dislocations whose edges exist at the film surface. In accordance with an etching model, the measured results of Langmuir probe suggest that the main influence mechanism of etching are the plasma density and electron temperature, and the increase of etching rate and deepening etch pits can be mainly attributed to the enhanced directional etching with rising ion flux and sheath voltage. Appropriate etching with oxygen plasma is an effective pretreatment method for enhancing the efficiency of rough polishing process in mechanical polishing of thick diamond film.     

Surface modification of polyether ether ketone (peek) films for flexible printed circuit boards

The surface of polyether ether ketone (PEEK) films was modified using plasma treatment, corona, or surface etching to improve their adhesion with regard to glued copper foils and copper layers generated by physical vapor deposition. After the pretreatments, surface chemical analysis was performed by X-ray photoelectron spectroscopy (XPS). The wetting behavior was qualitatively investigated by contact angle measurements. Surface topography was monitored by laser scanning microscopy (LSM). After coating, the adhesion strength of the copper layer was measured by a peel force test. Plasma treatment, corona discharge, or etching lead to a significant increase in adhesion. This increase is caused by a change in surface topography as well as by the incorporation of polar groups into the surface.