Laser-Induced Selective Metallization on Polymer Substrates Using

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Laser-Induced Selective Metallization on Polymer Substrates using Organocopper for Portable Electronics Jihai Zhang, Jin Feng, Liyang Jia, Huiyuan Zhang, Gaixia Zhang, Shuhui Sun, and Tao Zhou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 19 Mar 2019 Downloaded from http://pubs.acs.org on March 19, 2019

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ACS Applied Materials & Interfaces

Laser-Induced Selective Metallization on Polymer Substrates using Organocopper for Portable Electronics Jihai Zhang,a,b Jin Feng,a Liyang Jia,a Huiyuan Zhang,a Gaixia Zhang, b Shuhui Sun,*,b and Tao Zhou*,a a State

Key Laboratory of Polymer Materials Engineering of China, Polymer Research Institute, Sichuan University, Chengdu 610065, China. b

Institut National de la Recherche Scientifique-Énergie Materiaux et Télécommunications, Varennes, Quebec J3X 1S2, Canada

*Corresponding

author.

E-mail

address:

[email protected]

[email protected] (S. Sun)

1 Environment ACS Paragon Plus

(T.

Zhou);

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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Abstract: Our work proposed a facile strategy for selective fabricating the precise metalized patterns onto polymer substrates through laser direct structuring (LDS) technology using organocopper compounds. The copper oxalate (CuC2O4) and copper acetylacetonate [Cu(acac)2]

which

acted

as

laser

sensitizer

were

first

introduced

into

acrylonitrile-butadiene-styrene (ABS) matrix for prepare LDS materials. After the activation with 1064 nm pulsed near-infrared (NIR) laser, the Cu0 (metal copper) was generated from the CuC2O4 and Cu(acac)2, and then served as catalyst species for the electroless copper plating. A series of characterizations were conducted to investigate the morphology and analyze the surface chemistry of ABS/CuC2O4 and ABS/Cu(acac)2 composites. Specially, the X-ray photoelectron spectroscopy (XPS) analysis indicated that 58.3% Cu2+ in ABS/CuC2O4 was reduced to Cu0, while this value was 63.9% for the ABS/Cu(acac)2. After 30 min electroless copper plating (ECP), the conductivity of copper circuit on ABS/CuC2O4 and ABS/Cu(acac)2 composites were 1.22 × 107 Ω−1·m−1 and 1.58 × 107 Ω−1·m−1, respectively. Moreover, the decorated patterns and near field communication (NFC) circuit were demonstrated by this LDS technology. We believe that this study paves the way for developing organocopper-based LDS materials, which has the potential for industrial applications. Keywords: Organocopper; polymer; laser activation; selective metallization; laser-induced.


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1. Introduction In recent years, selective metallization on nonconductive polymer materials has received extensive investigations due to the broad applications in the fields of integrated microelectronic and aesthetic decoration.1-24 Generally speaking, the main approaches for the fabrication of metalized patterns are photolithography,5,

25

ink printing,7,

15, 24, 26-29

screen

printing,19 ligand-induced electroless plating (LIEP),30, 31 laser-assisted deposition, laser direct structuring (LDS), etc. Over the past decades, the photolithography technique was a dominant industrially available method for surface patterning of substrates. However, photolithography had several inevitable disadvantages, such as time-consuming, requiring expensive equipment and harsh manufacture condition. By comparison, ink printing is simple and efficient, and therefore, is suitable for fabricating patterns on a variety of substrates.8, 32, 33 Nevertheless, this method also has several general drawbacks, including the need of appropriate conductive inks, the design of feasible nozzle, relatively low conductivity, poor adhesion property between conductive layer and substrates and high sintering temperature.26, 27, 34 Similarly, the screen printing also needs to synthesize inks and necessary mask for obtaining the patterns. Meanwhile, it is difficult for screen printing to obtain high-precision patterns. For the ligand-induced electroless plating (LIEP) process, it always needs covalently grafting the chelating film onto the substrate and chemically reduced metal ions as the catalyst for electroless deposition. Therefore, developing a cost-effective and environmentally friendly method for the fabrication of metalized patterns in industrial applications is highly desired, while it remains challenging. Nowadays, the booming laser technology has been widely investigated in laser patterning,35-37 surface modification,38 medical treatment,39, 3 Environment ACS Paragon Plus

40

laser-assisted depositions,18


laser-induced forward transfer (LIFT),41 laser direct structuring (LDS), and so on.42-46 Among these, LDS is an innovative technology that holds promising potential for fabricating metalized patterns on non-conductive substrates with excellent design flexibility and high-precision.47 Moreover, this LDS technology can be used to fabricate molded interconnect devices (MIDs) with industrial scale for the pursuit of miniaturization in electronic devices. Although there have many types of laser (1064 nm, 532 nm, 355 nm), the 1064 nm pulsed near-infrared laser is always used for LDS technology from a practical and economic point of view. This is because the 1064 nm laser system is the most mature and inexpensive, which has been widely used in industry. It is worth mentioning that common polymers have no availability for LDS technology. To solve this problem, incorporating particular laser sensitizers that can generate catalytic seeds after laser activation in the polymer matrix is crucial for achieving a successful and excellent selective metallization. Therefore, laser sensitizers are important for fabricating LDS materials and optimization of LDS technology. To date, considerable efforts have been focused on inorganic copper compounds, such as copper-chromium oxide (CuO·Cr2O3),47 copper aluminum oxide (CuAl2O4),48 copper hydroxyl phosphate [Cu2(OH)PO4].49 Besides, copper-free laser sensitizer of antimony-doped tin oxide (ATO) and carbon materials of multi-walled carbon nanotube (MWCNT) were also used for LDS technology.50, 51 Are there other types of laser sensitizers available for LDS technology? Very recently, after numerous attempts, we have occasionally discovered that organocopper compounds could also be used to make LDS materials for LDS technology. According to the literature, organocopper compounds are widely used in catalysts and pharmaceuticals; however, their application in laser sensitizer has rarely been reported. From 4 Environment ACS Paragon Plus

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the perspective of molecular structure, organocopper contains at least one chemical bond between a carbon atom of an organic molecule and a copper atom.52 As the most common organic copper compounds, commercially available copper oxalate (CuC2O4) and copper acetylacetonate [Cu(acac)2] were selected as potential laser sensitizer for LDS investigation. Figure 1 presents the primary process of organocopper compounds-based LDS technology, which includes injection molding of polymer composites, the desired area of selective laser activation, and metallization. Specifically, CuC2O4 or Cu(acac)2 as laser sensitizers were firstly added into the polymer matrix to fabricate the so-called LDS materials, respectively. Then, the designed LDS materials performed the selective laser activation by the computer-controlled laser system to fabricate micro-rough structure and catalytic sites on the desired surface area, followed by electroless copper plating. In general, electroless plating is widely used in polymer metallization.11, 12, 27 Importantly, the selective surface activation is the necessary step for the selective electroless copper metallization.17 During the ECP process, the copper ions (Cu2+) in solution are gradually reduced by formaldehyde in the presence of catalytic sites. Subsequently, the redox reaction was carried out with the autocatalysis effect of copper. Moreover, copper has comparable conductivity to silver, while it has lower cost and better electromigration resistance than silver. This LDS technology dramatically simplifies the manufacture of metalized patterns and suitable for industrial production. In this study, CuC2O4 or Cu(acac)2 are incorporated into ABS matrix for prepare LDS materials, respectively. To our knowledge, this is the first systematically investigation of organocopper compounds laser sensitizer for LDS technology. The results demonstrated that under near-infrared (NIR) laser irradiation CuC2O4 and Cu(acac)2 were decomposed into 5 Environment ACS Paragon Plus


element copper (Cu0) particles, which acted as catalysis sites for the ECP. The obtained copper patterns exhibit high electrical conductivity and excellent mechanical adhesion, which is suitable for applications in circuit and decoration. Moreover, the near-field communication (NFC) device has also been demonstrated by integrating the copper circuit patterns and commercial integrated circuit (IC) chip for information writing and reading with a smartphone.

Figure 1. Fabrication process of organocopper compounds-based laser direct structuring (LDS) technology. 2. Experimental Section 2.1. Materials Copper oxalate (CuC2O4) and copper acetylacetonate [Cu(acac)2] were purchased from Shanghai Yueyuan Industrial Co., Ltd. The characterizations of CuC2O4 and Cu(acac)2 in spectroscopy and morphology are exhibited in Figures S1-S4 (Supporting Information). Analytical reagent grade of copper sulfate (CuSO4), formaldehyde (HCHO, 37 wt.% solution in water), potassium sodium tartrate (KNaC4H4O6·4H2O), ethylene diamine tetra-acetic acid


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(EDTA, C10H16N2O8), sodium citrate (Na3C6H5O7·2H2O), methanol (CH3OH), sodium hydroxide (NaOH), and absolute ethanol (CH3CH2OH) were bought from Chengdu Kelong Reagent. Acrylonitrile-butadiene-styrene (ABS, PA-747) resin was provided by Chi Mei Corporation. All the chemicals were used without any further purification. 2.2. Preparation of ABS/CuC2O4 and ABS/Cu(acac)2 Composites ABS resins incorporated with 5 wt.% CuC2O4 or 5 wt.% Cu(acac)2 was firstly mixed uniformly using a high-speed mixer, respectively. Then, the melt blending was performed at 200 °C using a twin-screw extruder. After that, plates with the dimension of 78 mm×65 mm×3 mm of ABS/CuC2O4 and ABS/Cu(acac)2 composites were fabricated at 200 °C using an injection molding machine. To ensure the copper layer to own good conductivity and adhesion property, as well as the efficiency for industrial applications, the content of organocopper compounds used in polymer composites was fixed at 5 wt.%. In Figure S5 (Supporting Information), it can be seen that CuC2O4 and Cu(acac)2 are thermally stable and almost have no decomposition within the processing temperature. To eliminate the inside stress, the as-prepared polymer plates were placed in the oven for 4 hours at 60 °C. 2.3. Laser Activation Before laser activation, the plates of ABS/CuC2O4 or ABS/Cu(acac)2 composites were ultrasonically treated in sodium hydroxide (1 M) solution for 5 min to remove surface contaminants, respectively. Then, the laser activation experiment was conducted using an optical fiber pulsed laser machine system (MK-GQ10B) in an air atmosphere. The laser machine equipped with a high precision digital galvanometer. Herein, the laser irradiation parameters were set by EZCAD 2.0 software. In the process of laser activation, the laser scanning speed was 400 mm·s−1, and the laser power was 8 W. The laser pulse frequency was 7 Environment ACS Paragon Plus


60 kHz, and the laser pulse width was 100 ns. More experimental details can be found in our previous literature reports.35 2.4. Metallization Before metallization, the laser-activated samples were ultrasonically cleaned with deionized water and alcohol for 5 min, respectively. The homemade ECP solution included copper sulfate (8 g/L) as the copper ion source, potassium sodium tartrate (30 g/L), sodium citrate (3 g/L), ethylene diamine tetra-acetic acid (3 g/L) as the complexing agent, formaldehyde (12 mL/L) as the reducing agent, and methanol (150 mL/L) as the stabilizer. The ECP experiments were conducted at 50 °C, and the ECP solution pH value was adjusted to 12.5 via NaOH. The deionized (DI) water was used for all experiments. 2.5. Fabrication of Near-Field Communication (NFC) Device The near-field communication (NFC) circuit with eight-turn square-shaped patterns (dimension: 32×32 mm, line width: 0.5 mm, adjacent line spacing: 0.5 mm) was obtained through LDS technology. Briefly, the NFC circuit was firstly fabricated via selective laser activation and metallization. Then, the 3M VHBTM double-sided tape was pasted onto the antenna coil as an insulating layer, and the Cu conductive tape was as an interconnect to bridge the solder pad and the antenna coil. Finally, the NFC chip (NXP NTAG216) was mounted onto the solder pads with Cu conductive tape. 2.6. Characterizations Fourier transform infrared (FTIR) spectrum was measured by a Nicolet iS50 spectrometer equipped with the attenuated total reflection (ATR) iTR accessory (ZnSe crystal). X-ray photoelectron spectroscopy (XPS) were analysed on a Kratos XASAM 800 spectrometer (Kratos Analysis) using Al Kα X-ray source (1486.6 eV). The binding energy scale was 8 Environment ACS Paragon Plus

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calibrated according to C 1s peak (284.6 eV) from CH2. Powder X-ray diffraction (PXRD) was carried out by an X-ray powder diffractometer (Rigaku, D/max-2500) operating at 40 kV and 40 mA with Cu Kα radiation (λ=0.15418 nm). The observation of optical microscope (OM) photographs was carried out using an Olympus BX-51 polarized optic microscope (POM) with the reflection mode. Field-emission scanning electron microscopy (FE-SEM) images were observed on a JEOL JSM-7500F machine equipped with an X-act electron for energy-dispersive

X-ray

spectroscopy

(EDX)

analysis.

Ultraviolet-visible-infrared

(UV-vis-IR) spectroscopy was performed on a UV-3600 (Shimadzu) spectrophotometer. Thermal gravimetric (TG) analysis was carried out using a thermal gravimetric analyzer (NETZSCH TG 209 F1). The contact angle (CA) measurement with the sessile drop method was measured using a Krüss K100. Scotch tape test (ASTM D3359) was conducted to evaluate the mechanical adhesion of copper layers. The electrical properties of the copper circuit were measured by Keithley 6487 picoammeter. 3. Results and discussion 3.1. Characterizations of Morphology In our experiments, the ABS/CuC2O4 and ABS/Cu(acac)2 composites were designed as LDS materials. Then, the LDS materials were molded into rectangular plates via injection molding for the convenience of the following characterizations and tests. To clearly assess the quality of the ECP, we fabricated the solid square blocks pattern (2 cm×2 cm). Note that, the distance between the line by line laser irradiation was set as 30 µm. As shown in Figure 2(a) and Figure 2(e), the laser-irradiated surface area appears clear boundaries, which is different from the un-irradiated area. This ability to form high-contrast marks on the polymer surface can also be used for laser patterning.35 Besides, the surface optical microscope (OM) images 9 Environment ACS Paragon Plus


show that both ABS/CuC2O4 and ABS/Cu(acac)2 appear micro-rough morphology which is caused by 1064 nm laser irradiation. Owing to this micro-rough structure, the surface contact

Figure 2. (a) Photograph and surface OM image of ABS/CuC2O4 after laser irradiation, scale bar: 200 µm. (b) Cross-sectional OM image of ABS/CuC2O4 after laser irradiation, scale bar: 100 µm. (c) Photograph and surface OM image of ABS/CuC2O4 after 30 min ECP, scale bar: 200 µm. (d) Cross-sectional OM image of ABS/CuC2O4 after 30 min ECP, scale bar: 100 µm. (e) Photograph and surface OM image of ABS/Cu(acac)2 after laser irradiation, scale bar: 200 µm. (f) Cross-sectional OM image of ABS/Cu(acac)2 after laser irradiation, scale bar: 100 µm. (g) Photograph and surface OM image of ABS/Cu(acac)2 after 30 min ECP, scale bar: 200 µm. (h) Cross-sectional optical microscope image of ABS/Cu(acac)2 after 30 min ECP, 10 Environment ACS Paragon Plus

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scale bar: 100 µm. angles (CA) of the samples are increased after laser irradiation, and the results are provided in Figure S6 (Supporting Information). The CA value of ABS/CuC2O4 after laser irradiation is increased from 87.1 ° to 102.8 °, and that of ABS/Cu(acac)2 after laser irradiation is enhanced from 86.8 ° to 103.5 °. In Figure 2(b) and Figure 2(f), the cross-sectional OM images indicate that the laser heat effect depth in ABS/CuC2O4 and ABS/Cu(acac)2 are 25.3 µm and 41.2 µm, respectively. Subsequently, from the photographs in Figure 2(c) and Figure 2(g), we observe that the selective metalized copper pattern is only obtained in the laser-irradiated area. Moreover, the surface optical microscope (OM) images indicate that the copper layers on both ABS/CuC2O4 and ABS/Cu(acac)2 have a high resolution. This phenomenon demonstrates that the laser-irradiated area has catalytic activity, which is curial to trigger the ECP process. The cross-sectional OM images reveal that the average thicknesses of the copper layer on ABS/CuC2O4 and ABS/Cu(acac)2 are approximately 6.35 µm and 5.61 µm, respectively. According to the above results, both CuC2O4 and Cu(acac)2 can be used as effective laser sensitizer for LDS. The following research is mainly morphology and physicochemical properties of laser activation and metallization. As shown in Figure 3, the FE-SEM observation was further conducted to analyze the surface morphology of the samples after laser activation and metallization. In Figure 3(a) and Figure 3(b), we observe that the sample surface appears complex micro-rough etching pits with small voids, which is due to the high-energy 1064 nm pulsed laser irradiation. This typical micro-rough structure facilitates the improvement of the adhesion strength between substrate and copper layer through microscale mechanical penetrating anchorage effect. It is



worth mentioning that morphologies of the laser-irradiated surface between ABS/CuC2O4 and ABS/Cu(acac)2 are different under the same laser activation conditions. In Figure S7 (Supporting Information), we performed the UV-vis-IR spectroscopy for the neat powders of CuC2O4 and ABS/Cu(acac)2. The UV-vis-IR analysis was to investigate the absorption of CuC2O4 and Cu(acac)2 at 1064 nm, where corresponds to the wavelength of NIR laser used in our work. It can be seen that the absorption of CuC2O4 is stronger than Cu(acac)2 at 1064 nm, which explains the different morphologies of the laser-irradiated surface between ABS/CuC2O4 and ABS/Cu(acac)2 composites. Moreover, the neat CuC2O4 and Cu(acac)2 before and after NIR pulsed laser irradiation was also investigated (Figure S8, Supporting Information). Compared to Cu(acac)2, the CuC2O4 has more obvious color changes under the laser irradiation, indicating a stronger absorption of 1064 nm laser.

Figure 3. SEM images of the samples after laser irradiation, scale bar: 100 μm, 10 μm. (a) ABS/CuC2O4; (b) ABS/Cu(acac)2. SEM images of the samples after 30 min ECP, scale bar: 100 μm, 10 μm and 1 μm. (c) ABS/CuC2O4; (d) ABS/Cu(acac)2. EDX test of the copper layer and the corresponding SEM, scale bar 100 μm. (e) ABS/CuC2O4; (f) ABS/Cu(acac)2. 12 Environment ACS Paragon Plus

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After 30 min ECP, in Figure 3(c) and Figure 3(d), the laser-activated area appears a thin layer of metallic copper. Besides, the corresponding magnified SEM images clearly demonstrate the uniform morphology of the copper layers, which are composed of aggregated copper particles. Note that, the copper layer morphologies on ABS/CuC2O4 and ABS/Cu(acac)2 are different, which reasonably explains the different color of the copper layer [Figure 2(c) and Figure 2(g)]. Furthermore, in Figure 3(e) and Figure 3(f), EDX analysis shows the characteristic bands of metal copper with L peak at 0.9 keV and K peaks at 8.0 keV and 8.9 keV. XRD measurements were also employed to characterize the composition and crystalline structure of the obtained copper layer, and results are shown in Figure S9. There are three clear Cu cubic structure features peaks arise at 2θ = 43.2 °, 50.4 °, and 74.1 °. Besides, no extra peaks appear in the XRD patterns, indicating that the obtained copper layer on ABS/CuC2O4 and ABS/Cu(acac)2 both possess a high purity.



Figure 4. XPS spectra and fitting results analyzed by XPSPEAK v4.0 software. (a) High-resolution Cu 2p spectra of neat CuC2O4 before and after laser irradiation; ABS/CuC2O4 composites after laser activation. (b) High-resolution Cu 2p spectra of neat Cu(acac)2 before and after laser irradiation; ABS/Cu(acac)2 composites after laser activation. 3.2. Characterizations of Spectroscopy To better understand the surface chemical composition of ABS/CuC2O4 and ABS/Cu(acac)2 composites, the XPS analysis was conducted. The sum function of the asymmetric Lorentzian-Gaussian was used to calculate, and curve fitting results are shown in Figure 4. Note that, the wide gray line denotes the sum of fitting peaks, the narrow black line denotes the raw data. As a kind of surface characteristic method, XPS analysis can investigate the chemical information of the material surface. The chemical valence state of copper (Cu) 14 Environment ACS Paragon Plus

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element is determined using the high-resolution Cu 2p spectra. Herein, the Cu2+ peaks appear at 953.6 eV (Cu 2p1/2) and 933.6 eV (Cu 2p3/2) along with their corresponding shake-up peaks around 937−947 eV and 958−965 eV, respectively. In Figure 4(b), for neat CuC2O4 before and after laser irradiation, the high-resolution Cu 2p spectra almost have no change. Similarly, in Figure 4(b), for neat Cu(acac)2 before and after laser irradiation, the high-resolution Cu 2p spectra also have no change. These results demonstrate the chemical valence of Cu in neat CuC2O4 and neat Cu(acac)2 doses not affected by laser irradiation. The possible reason is the lack of reducing conditions to reduce CuC2O4 and Cu(acac)2. Also, the presence of oxygen in an air atmosphere probably prevents the reduction of CuC2O4 and Cu(acac)2 to Cu0 (element copper) particles. However, for the ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser activation, there are two new peaks appear at 952.3 eV (Cu 2p1/2) and 932.5 eV (Cu 2p3/2), which are ascribed to Cu0 (element copper). Besides, we calculated the fitting area of the Cu 2p3/2 (932.5 and 933.6 eV) peak after laser activation. The results demonstrate that 58.3% Cu2+ in ABS/CuC2O4 and 63.9% Cu2+ in ABS/Cu(acac)2 are reduced to Cu0 (element copper), respectively. The produced Cu0 after laser activation serves as catalyst species to trigger the



Figure 5. (a) ATR FTIR spectra of pure ABS without laser irradiation; ATR FTIR spectra of ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser irradiation. (b) Surface micro-Raman spectra of pure ABS without laser irradiation; surface micro-Raman spectra of ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser irradiation. (c) Schematic illustrating the mechanism during laser activation and selective metallization. autocatalytic ECP. In the process of laser activation, the ability of laser sensitizers to reduce to Cu0 depends on two main factors. The first is the laser absorption capacity, and the second is the ability of the sensitizer itself to perform photochemical reduction reaction. The second factor is more important. A relative high laser absorption does not mean a high reduction


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efficiency of laser sensitizers. The enough Cu0 cannot be obtained when the ability of a sensitizer itself to perform photochemical reduction reaction is low, even if the sensitizer has a relatively high absorption. From the UV-vis-IR spectra (Figure S7), we observe that CuC2O4 has a stronger absorption than Cu(acac)2 at 1064 nm. However, the fitting results of XPS indicate that the more Cu0 generation in ABS/Cu(acac)2 than ABS/CuC2O4. That is to say, the reducing efficiency of Cu(acac)2 using laser energy is higher than that of CuC2O4, because Cu(acac)2 can be reduced to more Cu0 with relatively less laser energy. Moreover, ATR FTIR measurement was also conducted to study the chemical groups changes of ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser irradiation. In Figure 5(a), we observe the appearing of a new band at 1725 cm−1 which corresponds to C=O groups after laser irradiation, and this is used to evaluate the surface oxidation of polymer materials.47 The main reason for this phenomenon is the thermal oxidation of polymer substrate occurring in the zone affected by laser heat. Moreover, the high-resolution C 1s spectra of ABS/CuC2O4 and ABS/Cu(acac)2 after laser activation were recorded in Figure S10 (Supporting Information). The peaks at 286.5 eV and 284.7 eV are ascribed to C≡N, C−C, C−H, and C=C groups. Besides, one small peak arises at 288.4 eV attributed to the −C=O group from the thermal oxidation caused by laser irradiation. In Figure 5(b), the typical Raman spectra of ABS/CuC2O4 and ABS/Cu(acac)2 composites clearly show the band of the amorphous carbon (1000–2000 cm−1). Note that, the temperature generated by NIR laser is high enough to lead to rapid carbonization for ABS resin. Therefore, the formation of amorphous carbon is due to the instantaneous high temperature caused by laser irradiation. Furthermore, the XPS analysis was also conducted to demonstrate the formation of amorphous carbon after laser activation. In Figure S11 (Supporting Information), the carbon contents of ABS/CuC2O4 and 17 Environment ACS Paragon Plus


ABS/Cu(acac)2 after laser irradiation are 83.72% and 85.03%, respectively. As is known, the key to achieving selective metallization in ECP is the selective activation.53 Liao et al.16 developed an efficient method to fabricate copper patterns through ink printing (silver nitrate inks) and electroless copper plating. Hou et al.2 fabricated the conductive copper pattern on sandpaper through a scribing-seeding-plating (SSP) method. They first used the 450 nm blue laser to irradiate the sandpaper surface to generate the ablated structure and hydrophilic groups. Then, Au as catalytic seeds was selectively deposited into the laser-etched area followed by electroless copper plating. Very recently, Liu et al.54 synthesized a novel photo-patternable polyimide, which could absorb the palladium ions and form pyridine–Pd (II) complex under UV irradiation. After that, the ECP was conducted to generate copper patterns. In Figure 5(c), we provide the mechanism during laser activation and selective metallization. Herein, the Cu0 comes from the reduction of CuC2O4 and Cu(acac)2 under laser irradiation, and the critical reduction environment is provided by amorphous carbon. Subsequently, in the process of ECP, the newly formed Cu0 acts as catalyst seeds to trigger the selective metallization. Note that, the amorphous carbon comes from the carbonization of ABS resin, and therefore, the CuC2O4 and Cu(acac)2 cannot be reduced to Cu0 in the absence of ABS matrix. 3.3. Applications and Prospect


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Figure 6. Digital photographs of the obtained copper circuit (length: 21 mm, width: 2 mm) with different ECP time; (a) ABS/CuC2O4; (e) ABS/Cu(acac)2. The corresponding resistance of the copper circuit with the increase ECP time; (b) ABS/CuC2O4; (f) ABS/Cu(acac)2. The resistance ratio (R/R0) of copper circuit (30 min ECP) with storage days; the R and R0 are the resistance at given day and 0 day; (c) ABS/CuC2O4; (g) ABS/Cu(acac)2. Metallized copper world map as a decoration application; (d) ABS/CuC2O4; (h) ABS/Cu(acac)2. The organocopper compounds-based LDS technology developed in this work holds a potential application for fabricating conductive circuit and decorative patterns. Figure 6(a) and Figure 6(e) are the digital photographs of rectangle copper patterns on ABS/CuC2O4 and ABS/Cu(acac)2 with the ECP different time. A clear metallic copper layer appears on the desired area of the polymer substrate after 10 min ECP. Figure 6(b) and Figure 6(f) illustrate the corresponding resistance of the copper circuit on ABS/CuC2O4 and ABS/Cu(acac)2. It is noted that the resistance of the rectangle copper pattern after only 5 min electroless copper plating is too large to be measured. This is because the copper is gradually deposited into the laser-activated area on the polymer substrate during electroless plating. At the initial stage of



only 5 min, the deposited metal copper is completely discontinuous and therefore cannot form a conductive path. With the extension of the ECP time, the continuity of the copper layer increases and the electrical resistance gradually reduces. After 30 min ECP process, the resistances of the copper circuit on ABS/CuC2O4 and ABS/Cu(acac)2 are 0.135 Ω and 0.118 Ω, respectively. Moreover, we calculated the conductivity of the copper layer. According to the cross-sectional images in Figure 2(d) and Figure 2(h), the copper layer has an average thickness of 6.35 μm and 5.61 μm on ABS/CuC2O4 and ABS/Cu(acac)2, respectively. Therefore, the conductivity of the copper layers on ABS/CuC2O4 and ABS/Cu(acac)2 are 1.22 × 107 Ω−1·m−1 and 1.58 × 107 Ω−1·m−1, respectively. These results are not achievable by using ink printing. The specific calculations of conductivity are provided in the Supporting Information. From the curves in Figure 6(c) and Figure 6(g), we can observe that the resistance of the obtained copper circuit slightly increases along with the extension of storage days. Moreover, after two weeks (14 days) storage, the resistance value of the copper circuit reaches a plateau and keeps stable. This phenomenon can be explained by the formation of oxidation layer on the sample surface. To determine the maximum accuracy of the obtained copper circuit, we tried to prepare a conducting wire as thin as possible. Under the premise of ensuring good electrical conductivity, the widths of the narrowest conducting wires prepared are 204.9 μm and 181.3 μm for ABS/CuC2O4 and ABS/Cu(acac)2 composites, respectively. The optical microscope photographs of these two conducting wires are provided in Figure S12 (Supporting Information). Besides, the standard scotch-tape test was conducted to evaluate the adhesion property of copper layer on the polymer substrate. In Figure S13 (Supporting Information), the deposited copper layer tightly adheres to the ABS substrate, and none of the 20 Environment ACS Paragon Plus

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cross-hatched squares are stripped after the scotch tape test, exhibiting the highest 5 B scale (ASTM D3359 standard). This result meets the requirement for industrial applications. To demonstrate its decoration versatility, in Figure 6(d) and Figure 6(h), we fabricated the high-resolution metalized world map on both ABS/CuC2O4 and ABS/Cu(acac)2 composites using the LDS technology. The metalized patterns can be easily designed in any form.

Figure 7. (a) Schematic of the fabrication process for near-field communication (NFC) device with LDS technology and an integrated circuit (IC) chip. (b) Photograph of the obtained copper patterns and NFC tag on ABS/Cu(acac)2 composites. (c) Photographs of the NFC device operations before writing information via NFC and retrieved by a smartphone. Further, we fabricated a functional NFC tag for data communication using the LDS technology based on the ABS/Cu(acac)2 composites. NFC device is a kind of wireless identity tags and sensors for electronic identification, contactless payment, and health care application. The fabrication process is schematically illustrated in Figure 7(a). The circuit patterns were firstly prepared through selective laser activation (see Video S1, Supporting Information). Then, the conductive copper circuit was obtained by electroless copper plating. In Figure 7(b), the new fabricated NFC tag is integrated by assembling a commercial IC chip into the 21 Environment ACS Paragon Plus


copper circuit. The OM images of the IC chip are shown in Figure S14 (Supporting Information). Note that, in Figure 7(c), the IC chip is empty before writing information. Accordingly, the functional tag allows the IC chip to store the website message of “Sichuan University” via NFC between the tag and NFC-enabled smartphone. After that, the website message can also be conveniently retrieved by an NFC-enabled smartphone (see Video S2, Supporting Information). Therefore, we successfully demonstrate the NFC tag application through LDS technology and the integration of the commercial IC chip. 4. Conclusions In summary, this study investigated the organocopper compounds of CuC2O4 and Cu(acac)2 for LDS technology using the 1064 nm pulsed NIR laser. Optical microscope and SEM images indicated that the polymer composites appeared the etched micro-rough morphologies at the laser-activated area, which provides riveting points for the subsequently selective metallization. XPS analysis demonstrated the new formation of the Cu0 on both surfaces of ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser activation. Moreover, it was calculated that 58.3% Cu2+ in ABS/CuC2O4 was reduced to Cu0, while this value was 63.9% for ABS/Cu(acac)2. The selective metalized copper layer was successfully fabricated on the desired position of ABS/CuC2O4 and ABS/Cu(acac)2 composites after 30 min ECP. The obtained copper layer exhibited an excellent mechanical adhesion property and conductivity, which was comparable to that of metal copper. Specially, the conductivity of the copper layers on ABS/CuC2O4 and ABS/Cu(acac)2 are 1.22 × 107 Ω−1·m−1 and 1.58 × 107 Ω−1·m−1, respectively. The adhesion property of copper layer reached a 5B level according to the adhesive tape test (ASTM D3359). In particular, any arbitrary metalized copper patterns can be conveniently designed 22 Environment ACS Paragon Plus

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by LDS technology, including the circuit and decoration patterns. Therefore, this study provides a guideline for the developing of organocopper compounds-based LDS materials for LDS technology. Moreover, the NFC tag has been demonstrated through LDS technology combining with the integration of a commercial IC chip, which has a broad application prospect. Supporting Information. FTIR spectroscopy, XPS survey spectra, PXRD pattern, SEM image, TG and DTG curves of CuC2O4 and Cu(acac)2; surface contact angles of ABS/CuC2O4 and ABS/Cu(acac)2 composites before and after laser irradiation; UV-vis-IR spectroscopy of CuC2O4 and Cu(acac)2; photos of laser irradiation of neat CuC2O4 and Cu(acac)2; XRD measurement of the obtained copper layer; XPS high-resolution C1s spectra and survey spectra of ABS/CuC2O4 and ABS/Cu(acac)2 composites after laser irradiation; scotch tape test of the obtained copper layer; optical microscope photographs of the narrowest conducting wires; optical microscope photograph of the IC chip; calculations of copper layer conductivity; the real-time video of selective laser activation; the real-time video of NFC writing and reading process. Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant Nos. 51773126, 51473104), Outstanding Youth Foundation of Sichuan Province (Grant No. 2017JQ0006), Natural Sciences and Engineering Research Council of Canada (NSERC), and State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2018-2-09). J. Z. gratefully acknowledges the scholarships from China Scholarship Council (File No. 201706240131). References 23 Environment ACS Paragon Plus


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