The effect of TiO2 morphology on the surface modification of poly (ethylene terephthalate) for electroless plating

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89?KN?m^?1. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.     

Surface modification of ABS by photocatalytic treatment for electroless copper plating

Surface roughness of acrylonitrile–butadiene–styrene (ABS) resin prior to metallization is treated generally with sulphuric/chromic acid system. However, the presence of chrominum (VI) ion imposes serious environmental problems. In this work, TiO₂ photocatalytic treatment was used to enhance the adhesion strength between the ABS surface and the electroless copper film. Effects of the TiO₂ content, irradiation time and UV power upon the surface topography, surface characterization and the adhesion strength were investigated. The results indicated that the surface hydrophilicity of ABS resin and the adhesion strength between the electroless copper film and ABS surface increased with an increase in the UV power and a prolongation in irradiation time, and did not increase linearly with an increase of TiO₂ content. Though the surface topography of ABS changed little, the adhesion strength reached 1.25?kN/m, which was higher than that in the optimal H₂SO₄–MnO₂ colloid. The surface chemistry results indicated that –COOH and –OH groups formed with the photocatalytic treatment and the absorption strengths increased with the UV power. XPS analysis results further demonstrated that the contents of C=O and –COOH reached 6.4 and 4.9% with the photocatalytic treatment, which was much higher than that of the H₂SO₄–MnO₂ colloid (3.9 and 3.1%). The high contents of C=O and –COOH groups enhanced the surface hydrophilicity of the ABS resin and improved the adhesion strength between the electroless copper film and ABS resin. The results indicated that the photocatalytic treatment was an environment-friendly and effective method to replace the commercial wet chemical process for ABS surface modification.     

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.     

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.     

Study of an environment-friendly surface pretreatment of ABS-polycarbonate surface for adhesion improvement

In this paper, an environmentally friendly etching system containing MnO₂–H₃PO₄–H₂SO₄ colloid was used to investigate surface etching for ABS- polycarbonate (PC/ABS) as a replacement for conventional chromic acid etching solutions. In order to obtain a good etching performance, a swelling system, containing tetramethylammonium hydroxide (TMAH), and 1-Methyl-2-pyrrolidinone (NMP), was used to investigate the surface swelling for PC/ABS resin. Then the effects of H₂SO₄ concentration, and etching time on the surface topographies and surface contact angle were investigated. After the optimal swelling and etching treatment, the surface contact angle of PC/ABS resin decreased from 95.7° to 28.3°, and the adhesion strength between electroless copper film and PC/ABS resin reached to 1.04 KN m⁻¹. The FT-IR spectra and XPS analyses indicated that hydroxyl and carboxyl groups formed on the PC/ABS surface as a result of the swelling and etching treatment, which improved the adhesion strength between PC/ABS substrate and elctroless copper film.     

Plasma surface modification of polyimide for improving adhesion to electroless copper coatings

The influences of oxygen plasma treatment of polyimide (PI) films on the adhesion of electroless copper coatings as well as on the chemical composition of the film surface and the PI surface morphology were investigated. The plasma operating parameters were 1800 W forward power with O₂ flowing at a rate of 300 cm³/min at a pressure of 200 mTorr. The peel strength increased with decreasing plasma treatment temperature. However, extension of the treatment time at higher temperatures had a positive effect on adhesion. A correlation between the enhancement in peel strength and the content of oxygen-containing groups at the PI surface (investigated using XPS) was observed. A change in the morphology as a result of plasma etching was also observed, in the formation of pits in the film surface. The pits ranged from 3 to 6 μm in depth and the diameter varied from 10 to 200 μm. Comparison of the data obtained after plasma treatment with the results of chemical etching in alkaline solutions of permanganate showed approximately the same adhesion increase (to 0.6 kN/m) in both cases. However, chemical etching did not affect the surface morphology and increased the oxygen content at the PI surface less than the plasma treatment.     

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.     

Adhesion improvement of electroless copper to PC substrate by a low environmental pollution MnO2–H3PO4–H2SO4–H2O system

A low environmental pollution etching system, MnO₂–H₂SO₄–H₃PO₄–H₂O colloid, was used to investigate surface etching performance of polycarbonate (PC) as a replacement for the chromic acid etching solution. The effects of H₂SO₄ concentrations, H₃PO₄ concentrations and etching times upon the surface topography, surface chemistry and surface roughness were studied. With the appropriate etching treatment, the surface average roughness (R_a) of PC substrates increased from 3 to 177 nm, and the adhesion strength between the electroless copper and PC substrate also reached 1.10 KN m⁻¹. After the etching treatment, the PC surface became hydrophilic and the surface contact angle decreased from 95.2° to 24.8°. The intensity of C–O groups increased and the new functional groups (–COOH) formed on the PC surface with the etching treatment, which improved the adhesion strength between PC substrate and elctroless copper film.     

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     

Adhesion improvement of electroless copper to a polyimide film substrate by combining surface microroughening and imide ring cleavage

In order to enhance the adhesion strength of copper metal film to a polyimide (PI) film substrate, a method combining surface microroughness formation and imide ring cleavage was investigated. The results showed that imide rings were cleaved with a KOH treatment while carboxyl and amide groups were formed on the surface of the PI film. The surface micro-roughness did not change with the KOH treatment, and the adhesion strength of the copper metal film to the PI film was slightly improved to 30 g/mm, which could be attributed to the interaction of both carboxyl and amide groups with the copper atoms. When the PI films were successively treated with an alkaline permanganate and a KOH solution, many recesses were formed on the surface in an alkaline permanganate solution, and the size and depth of the recesses increased with alkaline permanganate treatment time. The results of the AFM measurements showed that the average roughness (R) increased from 3.54 to 10.23 nm after combined treatment with alkaline permanganate and KOH solutions. The adhesion strength of the copper metal film to the PI film reached 150 g/mm, which was five times greater than that achieved with the KOH treatment only.     

Supercritical fluid‐assisted electroless metal plating onto aramid films: The influence of thermal treatment

Although the production of electro‐conductive aramid fibers is efficient, the method needs to be modified before it can be applied to aramid films. Whereas impregnation of an aramid film with a metal complex using supercritical CO₂ is achievable, the relatively low adhesion strength of the metal layer applied using electroless copper plating is problematic. To solve this problem, thermal treatment was conducted before, after, or both before and after electroless plating. The rationale for using thermal treatment to improve the adhesiveness of the plated layer was based on the findings that (1) an aramid film contains a significant amount of water (about 3.5 % w.o.f.), which might have a negative impact on adhesion; and (2) because an impregnated metal complex liberates metal catalyst by thermal decomposition during impregnation, a supplementary thermal action might liberate more catalyst and thereby improve adhesion. We found that thermal treatment improved adhesion of the metal layer to the aramid film. Moreover, we discovered that with respect to electroless copper plating, a short time‐lag was crucial to obtaining a thin and homogeneous metal layer with strong adhesion. In addition, we demonstrate the affinity of an aramid film for Pd(acac)₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photocatalytic activity of undoped and sulfur-doped TiO2 films grown by MOCVD for water treatment under visible light

Titanium dioxide ceramic coatings have been used as catalysts in green technologies for water treatment. However, without the presence of a dopant, its photocatalytic activity is limited to the ultraviolet radiation region. The photocatalytic activity and the structural characteristics of undoped and sulfur-doped TiO₂ films grown at 400 °C by metallorganic chemical vapor deposition (MOCVD) were studied. The photocatalytic behavior of the films was evaluated by methyl orange dye degradation under visible light. The results suggested the substitution of Ti⁴⁺ cations by S⁶⁺ ions into TiO₂ structure of the doped samples. SO₄^2? groups were observed on the surface. S-TiO₂ film exhibited good photocatalytic activity under visible light irradiation, and the luminous intensity strongly influences the photocatalytic behavior of the S-TiO₂ films. The results supported the idea that the sulfur-doped TiO₂ films grown by MOCVD may be promising catalysts for water treatment under sunlight or visible light bulbs.     

Electroless plating of copper on polyimide films modified by surface grafting of tertiary and quaternary amines polymers

Argon plasma-pretreated polyimide (PI, Kapton^® HN) films were subjected to UV-induced surface graft copolymerization with N,N′-(dimethylamino)ethyl methacrylate (DMAEMA) and 2-(trimethylammonium)ethyl methacrylate chloride (TMMAC). The DMAEMA graft-copolymerized PI (DMAEMA-g-PI) surfaces were also quaternized and amino-functionalized with 3-bromopropylamine hydrobromide (the Q-DMAEMA-g-PI surfaces). The surface composition and the degree of quaternization of the graft-modified PI films were determined by X-ray photoelectron spectroscopy. The DMAEMA-g-PI, Q-DMAEMA-g-PI and TMMAC graft-copolymerized PI (TMMAC-g-PI) surfaces can be activated directly by PdCl₂, in the absence of prior sensitization by SnCl₂ (the ‘Sn-free’ activation process), for the subsequent electroless plating of copper. A shorter induction time for the electroless deposition of copper was found for the palladium-activated Q-DMAEMA-g-PI and TMMAC-g-PI surfaces than for the palladium-activated DMAEMA-g-PI surface. The T-peel adhesion strength of the electrolessly deposited copper with the Q-DMAEMA-g-PI surface was enhanced to above 6 N/cm, in comparison to only about 4 N/cm for the DMAEMA-g-PI surface, about 2.5 N/cm for the TMMAC-g-PI surface, or about 0.5 N/cm for the PI surface with argon plasma treatment alone.     

Study on the pretreatment method of glass-epoxy resin in the presence of TiO2 sol prepared by hydrothermal method

In the present study, the pretreatment of glass-epoxy resin using photoreaction of TiO₂ sol prepared by hydrothermal method was investigated. The surface properties for the pretreated substrate were examined, and the change of contact angle was measured to confirm the hydrophile property caused by the photocatalytic reaction. After the pretreatment, the surface was oxidized with showing no changes in its morphology. However, the surface roughness at nano-scale order increased with the photocatalytic reaction time. When UV light was irradiated for 60 min in TiO₂ sol, the adhesion strength of electroless-plated Cu film was most excellent in other test conditions.     

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     

Photocatalytic hydrogen production from methanol aqueous solution under visible-light using Cu/S–TiO2 prepared by electroless plating method

Cu was loaded on the S-doped TiO₂ by electroless plating method. The prepared Cu/S–TiO₂ exhibited high photocatalytic activity for hydrogen generation, and the yield is up to 7.5 mmol h^− 1 g^− 1cat in methanol solution. Their physical structure and chemical properties were characterized by UV–Vis, XRD, XPS and EXAFS. The copper species were CuO and Cu₂O, and the sample showed excellent visible light absorption ability. Comparing with the sample prepared by chemical reducing method, the electroless plated copper on S–TiO₂ was highly dispersed, which could facilitate photo-generated charges capture, transfer and separation.     

Characterization of Cu Nanoparticles on TiO2 Photocatalysts Fabricated by Electroless Plating Method

Cu-modified TiO₂ photocatalysts (Cu/TiO₂) were fabricated by electroless plating and wet impregnation methods. Photocatalytic activity for H₂ production over Cu/TiO₂ by electroless plating method was higher than that over Cu/TiO₂ by impregnation method. Characterization of Cu nanoparticles by HRTEM, STEM-EDX, XRD and XAFS was studied. As compared to the wet impregnation method, the electroless plating method resulted in the formation of Cu nanoparticles with small size and uniform distribution on the TiO₂ surface, which caused the enhancement of H₂ production. XAFS measurement provided the evidences for the chemical state change of Cu species during the photocatalytic reaction. The process that Cu species varied from Cu²⁺ into Cu⁰ via Cu¹⁺ as the intermediate under photoirradiation is very important for the H₂ production, which indicates that the metallic Cu nanoparticles acted as the active sites and restrained the photogenerated charges recombination.     

Oxidation of the copper alloy with pure copper plating

The oxidation failure of a copper alloy lead frame with/without a copper plating layer was investigated. The oxidation rate and adhesion strength of oxide films on copper alloy substrates were studied by measuring the thickness and by carrying out peel tests. The adhesion strength of the oxide film was mainly influenced by the composition but not the thickness of the oxide film. The highest adhesion strength was obtained when the oxide film was composed mainly of Cu₂O. When the thickness of the copper preplated layer was over 0.165?μm, the Cu atoms of the preplated copper were available for oxidation. Thus the oxidation process was within the copper preplated layer, and the main product of the oxidation was Cu₂O. It was found that the large column grain of the oxide film on the copper alloy with a copper plated layer, favored the diffusion of copper or oxygen atoms that led to the formation of Cu₂O, and lead to higher adhesion strength. This indicated that the oxidation resistance of a copper alloy lead frame can be effectively improved by electroplating copper.     

Influence of Metal (Au, Ag) Micro-Grid on the Photocatalytic Activity of TiO2 Film

In this paper, we prepared TiO₂ thin film with the surface modified by a connected Au micro-grid via a microsphere lithography strategy, and the modified films show higher photocatalytic activity than the pure TiO₂ film. The photocatalytic activity improved as Au loading increased, obtaining the best performance at a certain loading amount, and then decreased at higher loading amount. This behavior, not observed in TiO₂ films modified with Ag micro-grid, can be attributed to the relationship between the energetic positions and the metal clusters size.     

Effect of TiO2 on thermal and adhesive characteristics of poly(imide siloxane)/TiO2 hybrid films

A novel poly(imide siloxane)/titania (PIS/TiO₂) hybrid film was fabricated by sol‐gel process via in situ formation of TiO₂ within PIS matrix. Poly(amic acid siloxane) (PAAS) was prepared from 4,4′‐oxydiphthalic anhydride, 2,2‐bis [4‐(4‐aminophenoxy) phenyl] propane, and α,ω‐bis(3‐aminopropyl)polydimethylsiloxane (APPS). Chelating agent, acetylacetone, and catalyst‐free polymerization were used to reduce the rate of hydrolysis of titanium alkoxide in the PAAS. X‐ray photoelectron spectroscopy data showed that the presence of APPS promotes the Ti surface composition of PIS/TiO₂ hybrid film. The effects of TiO₂ and APPS contents on the characteristics of surface, thermostability, coefficient of thermal expansion (CTE), and the strength of adhesion were investigated. The presence of TiO₂ on the surface of the hybrid films enhanced the adhesive strength at the interface of PIS/TiO₂ hybrid film and copper foil. When more TiO₂ was incorporated into the PIS matrix, the PIS/TiO₂ hybrid film exhibited lower CTE while retaining favorable mechanical and thermal properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012