Fabrication of super-hydrophobic nano-sized copper films by electroless plating

Super-hydrophobic nano-sized copper films were fabricated on smooth glass substrates by an improved electroless plating technology. The copper film deposited for 1 min showed extremely high hydrophobicity with a water contact angle of 138.0^o and super-hydrophobicity with a water contact angle of 152.4^o when it was modified with 1-octadecanethiol (CH3-(CH2)17-SH). Such super-hydrophobicity is attributed to the combined roles of the surface hierarchical structure consisting of the micro-sized island-shaped agglomerates that are composed of the nano-sized copper nodules and the low surface energy formed through the chemical modification.     

A novel technique for fabrication of metallic structures on polyimide by selective electroless copper plating using ion implantation

The successful use of palladium ion implantation into polyimide to seed an electroless plated film of copper on the polyimide surface is reported. Polyimide (Hitachi PIX 3400) was implanted with palladium ions to doses of 1.5 × 10¹⁵ − 1.2 × 10¹⁷ ions cm⁻² using a MEVVA ion implanter. The implanted ions acted as sites for nucleation of copper film. A copper film was then deposited on implanted polyimide using a commercial electroless plating solution. The ion energy was kept low enough to facilitate a low critical ‘seed’ threshold dose that was measured to be 3.6× 10¹⁶ Pd ions cm⁻². Test patterns were made using polyimide to study the adaptability of this technique to form thick structures. Plated films were studied with optical microscopy, Rutherford Backscattering Spectrometry (RBS) and Profilometry. The adhesion of films was qualitatively assessed by a ‘scotch tape test’. The film growth (thickness) was observed to be linear with plating time. A higher implantation dose led to greater plating rates. The adhesion was found to improve with increasing dose.     

Microstructure and thermal decomposition property of Ni-P/Cr2N composite powder by electroless plating

Cr₂N is the most promising blowing agent for the preparation of steel foam using melt foaming method. In this work, to obtain a blowing agent with suitable density and gas decomposition characteristics for steel melt foaming, Ni-P/Cr₂N composite powder was prepared by electroless plating. The surface morphology, phase, coating thickness, density and decomposition characteristics of Ni-P/Cr₂N composite powder were analyzed. The results indicate that the surface of Ni-P/Cr₂N composite coating powder is covered by the high nickel and low phosphorus layer which has a dense and uniform cell structure. The decomposition rate of the Ni-P/Cr₂N composite powder is 7.46?mW/mg slower than that of the uncoated Cr₂N powder at 1107.4?°C. When the plating time is 30?min, the thickness of Ni-P layer reaches 2.86?μm, the density of the Ni-P/Cr₂N composite powder is 7.45?g/cm³, and maximal decomposition rate temperature reaches 1500?°C. These findings suggested that Ni-P/Cr₂N composite powder meets the requirements of decomposition temperature and density of the blowing agent used to produce steel foam with a uniform pore structure by the melt foaming method.     

The wear and arc erosion behavior of novel copper based functionally graded electrical contact materials fabricated by hot pressing assisted electroless plating

In this study, hot pressing was used to fabricate the novel copper based functionally graded electrical contact materials synthesized by silver, nickel and chrome plated copper core particles. For the fabrication of functionally graded materials (FGMs) by hot-pressing; pure copper, two and three layered metallic powders were used in the lower, middle and upper layer, respectively. The wear and arc-erosion performances of the developed materials increased from 3 to 10 times as compared to that of pure copper. Wear tests showed that the abrasive wear mechanism was dominant for the FGMs including electroless nickel and chromium coating layer. The highest specific wear rate (SWR) value was found in Cu_f-Ag′ (4.9 × 10⁻⁴ mm³/Nm) materials under the load of 20 N while the lowest SWR value belongs to Cu_f-Ag-Ni′ (2.3 × 10⁻⁴ mm³/Nm) materials under the load of 10 N. While severely melted and deformed regions are dominant on arc erosion surfaces of pure copper and copper-silver containing contacts, flatter and relatively less melted regions were detected on the surfaces of FGMs containing nickel and chromium. The arc-erosion loss values (cm³ × 10⁻⁴) measured for FGM₁ sample were 0.75 and 0.70, 0.99 and 0.88, 1.21 and 1.04 at 3000 cycles under the current of 5 A, 10 A and 15 A in fixed and moving contacts, respectively.     

Study of a pre-treatment process for electroless copper plating on ceramics

In this paper, a pre-treatment process for electroless copper plating on the ceramics was explored. Due to the catalytic activity of gold nanoparticles, the traditional three-step coarsening-sensitization-activation pre-treatment process has been optimized to a two-step coarsening-activation process. In our study, the following results were observed: electroless copper coating on the ceramics was formed after activating the substrate by gold nanoparticles; a more flat and compact nano-composite coating was also obtained by adding gold nanoparticles to the plating solutions. The mechanisms of pre-treatment and composite plating with gold nanoparticles were discussed.     

Improvement of Ta-based thin film barriers on copper by ion implantation of nitrogen and oxygen

Magnetron sputtered polycrystalline Ta and Ta(Si) barriers for copper metallization schemes were modified by nitrogen as well as oxygen high dose ion implantation to improve their thermo-mechanical stability. Ion bombardment changed the initial polycrystalline microstructure to amorphous-like. In contrast to pure Ta, Ta(Si) layers were already amorphous or nanocrystalline after deposition. In this case, the annealing temperature at which formation of a well crystallized structure occurs increased by approximately 100 K as a result of the implantation. In order to demonstrate the improvement in the barrier properties of the implanted Ta films, the intermixing of Ta and Cu at the interface of corresponding layer structures was measured as a function of the annealing temperature by depth profiling using Auger electron spectroscopy (AES). The thermal stability of Ta and Ta(Si) barriers increased from 600 °C/1 h for the non-implanted layers up to 750 °C/1 h after implantation of nitrogen or oxygen.     

Facile electroless copper plating on diamond particles without conventional sensitization and activation

Conventional electroless plating of copper on diamond particles needs SnCl₂ sensitization and PdCl₂ activation pretreatments, which needs noble metal and consumes a large amount of reducing agent. In this paper, metallic tungsten coatings were first plated onto diamond particles by microwave-heating salt-bath plating (MHSBP) method, and then copper layer was directly plated onto the out surface of the tungsten layer by an electroless plating method with no need of SnCl₂ sensitization and PdCl₂ activation pretreatments. Composition and morphology of the coatings was analyzed by XRD, SEM, and EDS. The results show that the copper coating on the diamond surfaces can be adjusted by control the concentration of CuSO₄·5H₂O and plating temperature, and a full copper coating is achieved with content of CuSO₄·5H₂O of 19.6 g/L in the plating solution at 60 °C. The bending strength of the coated diamond/Cu composites is as high as 630 MPa, which increases 93.3% than the uncoated composites. This work presents an electroless plating of copper can directly on the surfaces of diamond particles with no need of conventional sensitization and activation, and a strong interface combination between coated diamond and copper.     

铜表面有机镀膜及薄膜性能研究

通过有机镀膜的方法,利用一种自设计合成的三嗪硫醇化合物(TTN)在铜表面制备有机薄膜.通过循环伏安法解释了TTN在纯铜表面的反应及有机薄膜(PTT)的生长过程,并在0.05mA/cm2的电流密度下进行恒电流有机镀膜.通过电化学方法对薄膜的性能进行了评价,测试结果显示有机镀膜方法能在铜表面获得均匀致密的有机膜,为有机介电薄膜的制备提供研究基础.     

Nickel coating on peptide nanotubes by electroless plating

A cyclic tri-β-peptide, cyclo(4-(4-pyridyl)-β-homoalanine)₃, was synthesized. The cyclic peptide was crystallized into μm-sized rods. Electron diffraction analysis revealed that the rod was composed of peptide nanotubes, which were formed by molecular stacking of the cyclic peptides, with nanotube alignment along the long axis of the rod. Ni coating of the rod crystals was carried out by electroless plating. The pyridyl groups at the side chains of the cyclic peptides were used for immobilization of Pd(II) ions on the surface as catalyst for the reduction reaction. The rod crystals were coated with Ni layers, but the electronic conductivity of the Ni-coated rods was found to be low probably due to the grain boundaries between Ni nanocrystals on the μm-sized rod surface.     

Optical propagation modified by Cu nanoparticle grating fabricated by heavy ion implantation

The optical propagation property of a planar waveguide with a periodic nanoparticle grating layer is characterized by using sliding prism method. Here, Cu nanoparticle grating was fabricated on a-SiO₂ substrate by periodic heavy-ion irradiation technique. The pitch of these gratings was 2 μm and 3 μm, respectively. The flux and fluence were at the range of 6-10 μA/cm² and 6 × 10¹⁶-1 × 10¹⁷ ions/cm², respectively. The grating effect, mainly including the mode selection effect, is observed. The effect depends on the pitch of the grating and the morphology of nanoparticles. The propagation loss of the waveguide induced by nanoparticle layer is evaluated.     

化学镀铜法制备纳米Cu-Al2O3复合粉体的研究

采用化学镀方法在超声波辐照下对10－20nm的Al2O3粉末进行化学镀铜，并探讨了镀液组成及工艺条件对纳米Al2O3粉末化学镀铜的影响，利用X射线衍射判断其成分组成，用TEM观察镀覆结果，结果表明：引入超声波并调整镀液组成和工艺条件可以实现室温的纳米Al2O3粉末化学镀铜，使化学镀鲷在低温下保持了镀液的稳定性，同时对纳米粉末进行有效的分散；以EDTA－2Na为络合剂，并加入亚铁氰化钾和2－2联吡碇作为稳定剂，可以有效地消除或减少复合粉末中的Cu2O.通过改变低温超声波化学镀铜时的镀液组成和装载量，可以一次镀覆得到铜含量为5％－90％的Cu-Al2O3复合粉末。     

A vacuum plasma surface pretreatment for refining seeding of Co in electroless copper plating

In this work, various vacuum plasma types, generated by either single gaseous sources (N₂ or H₂) or mixed sources (N₂-H₂) are incorporated into an aqueous-solution electrochemical seeding process to pre-treat the surfaces of SiO₂ dielectric layers. Under the optimal plasma atmosphere (monitored by optical emission spectroscopy), the dielectric surfaces can be modified to terminate by hydrophilic bonds, accelerating the adsorption of a crowd of catalytic seeds as small as 3 nm. Such a seeding refinement allows for the growth of a Co-based barrier layer with thickness as thin as 10 nm using electroless plating. Moreover, the capacity of integrating the plasma surface pretreatment with the seeding and electroless-plating process steps to deposit an ultrathin copper-stacked metallization layer in a selective and sequential manner on blanket wafers will be demonstrated by the fabrication of copper-gated and barrier-interposed capacitors. Finally, a tentative work of filling the seeds and the barrier layer into trenches of a patterned wafer was carried out, demonstrating the potential of the reported technique for advanced technology nodes of 60 nm or less.     

Fabrication of silica/platinum core-shell particles by electroless metal plating

An electroless metal plating method was used to form Pt shells on sub-micrometer-sized silica (SiO₂) particles fabricated by a sol-gel method. The electroless metal plating method was comprised of three steps: (1) surface-modification of SiO₂ particles with polyvinylpyrrolidone (PVP) (SiO₂/PVP) or poly-diallyldimethylammonium chloride (PDADMAC) (SiO₂/PDADMAC), (2) pre-deposition of Pt nuclei or Pt fine particles on the SiO₂ particles by reducing Pt ions in the presence of SiO₂/PVP particles (SiO₂/PVP-Pt) or SiO₂/PDADMAC particles (SiO₂/PDADMAC-Pt), and (3) growth of the pre-deposited Pt by immersing the SiO₂/PVP-Pt or SiO₂/PDADMAC-Pt particles in a Pt-plating solution. The pre-deposition of Pt nanoparticles was successfully performed for the surface-modified SiO₂ particles since the surface modification possibly strengthened the affinity between the SiO₂ particle surfaces and Pt ions. The Pt nanoparticles were pre-deposited more uniformly in the case of PVP because the pre-deposition took place more slowly for the PVP, which provided uniform surface-modification followed by the uniform pre-deposition of Pt nanoparticles. The formation of Pt shells was successfully performed on the SiO₂/PVP-Pt particles in the electroless metal plating process because Pt nuclei were generated by the reduction of H₂PtCl₆ and then further deposited on the Pt particle surfaces on the SiO₂/PVP-Pt particles.     

Optical nonlinearity of metal nanoparticle composites fabricated by negative ion implantation

Optical absorption and nonlinear absorption were studied for Ag nanoparticle composite. Negative Ag⁻ ion with 60 keV were applied for implanting into amorphous-SiO₂ at a flux 3 μA/cm² to total fluences ranging from 3 × 10¹⁶ to 1 × 10¹⁷ ions/cm². Absorption spectra of Ag-implanted amorphous-SiO₂ showed a surface plasmon peak resulting from formation of nanoparticles. The strength of the resonance reflected from the local electric field inside the nanoparticle induced by an external electric field. Nonlinear optical constants were evaluated by the z-scan method with a tunable femtosecond laser system. The strength of the nonlinearity also reflected from the local electric field. Nonlinear absorption coefficients exhibit a maximal value of −3.6 × 10³ m/GW for Ag:SiO₂ at 420 nm (2.95 eV), around the surface plasmon resonance.     

氧化铝陶瓷局部活化及选择性化学镀铜的研究

为解决陶瓷表面局部化学镀存在的问题,研制了一种针对氧化铝陶瓷局部化学镀铜前处理用的活化胶,其由具有活化能力的银盐(或钯盐)和粘稠的复合物有机载体组成.将活化胶印于氧化铝陶瓷表面,经500℃高温烧结形成局部活化层后,可直接置于化学镀液中进行镀铜处理,得到与印刷图形一致的局部镀铜层.利用电化学工作站测定样品在化学镀铜溶液中电位随时间的变化情况,考察不同活化条件对Cu2+还原的催化活性,利用SEM/EDS进行表面形貌及成分分析,确定了活化胶中银盐和钯盐的适宜浓度.结果表明,该两种活化胶应用于氧化铝陶瓷表面化学镀铜的活化工艺,可实现敏化活化的一步化,使陶瓷表面局部化学镀工艺流程简化,成本降低,具有较高的实用价值.     

The effect of titanium ion implantation into carbon ceramic on its wettability by liquid copper

There is a growing interest in the carbon ceramics and their use in present technology. Among other problems, the joining of such ceramics with other materials presents an important challenge. Since joining with metals is associated with wetting, we studied the effect of ion implantation on wetting of various forms of carbon and of silicon carbide by copper. An essential result is that Ti ion implantation followed by ArcPVD Ti deposition results in excellent wettability in all studied cases.     

Microstructure of interface for high-adhesion DLC film on metal substrates by plasma-based ion implantation

The diamond-like carbon (DLC) film was prepared on various metal substrates with a plasma-based ion implantation and deposition using superimposed RF and negative high-voltage pulses. The adhesion strength of DLC film was enhanced above the epoxy resin strength by implantation of carbon ions or mixed ions of carbon and silicon to the substrate surface before DLC deposition. In order to clarify the mechanism for improvement in adhesive strength, the microstructure of an interface between DLC film and substrate was examined in detail by transmission electron microscopy (TEM) observations in combination with EDS analysis. As a result, the enhancement in adhesion strength of DLC film by C ion implantation resulted from the formation of amorphous-like phase in the ion-implanted region of substrate, the production of carbon-component graded interface, the destruction of the oxide layer on the top surface of substrate, and the reduction of residual stress in DLC film by ion implantation during the deposition. The production of stress-free DLC film allowed us to demonstrate a supra-thick DLC film of more than 400 μm in thickness.     

Planar optical waveguides in Nd:BSO crystals fabricated by He and C ion implantation

Planar optical waveguides in Nd:BSO crystals were fabricated by the implantation of 500 keV He ions and 6.0 MeV C ions at two different substrate temperatures. The guiding modes were measured by the prism-coupling method with a He-Ne beam at 633 nm. The intensity calculation method (ICM) and reflectivity calculation method (RCM) were used for reconstructing refractive index profiles. The near-field intensity distribution of the waveguide, formed by He and C ions implanted after annealing at 300 °C, was measured by the end-face coupling setup. It was in reasonable agreement with the intensity of the waveguide mode simulated by the finite-difference beam propagation method (FD-BPM). The absorption spectra of the sample with He ions implanted at fluences of 3 × 10¹⁶ ions/cm² were measured using a spectrophotometer.     

Refractive indices and thicknesses of optical waveguides fabricated by silicon ion implantation into silica glass

Planar optical waveguides formed by Si ion implantation into PECVD SiO₂ have been characterized by the dark mode spectroscopy method at a wavelength of 0.6328 μm. The measured effective index values of the guided modes have been used to investigate the optical properties of the core layers of the waveguides after different pre-implantation treatments. It was found that annealing the specimens before implantation, affected both the refractive index and thickness of the core layers. In the annealed specimens a thicker core layer and a larger relative refractive index difference between the core and the buffer layer resulted.     

改性塑料表面亚铜化合物的表征及催化化学镀铜作用

在PC/ABS熔融共混的聚合物中掺杂Cu基金属化合物制得改性塑料,运用适当激光参数活化其表面,对此改性塑料表面进行化学镀铜.利用扫描电镜(SEM)、X射线能谱分析(EDS)、X射线光电子能谱分析(XPS)及电子显微镜对其活化层进行表征,结果表明:活化层中Cu元素以亚铜离子(Cu+)的形式构成亚铜化合物.亚铜离子(Cu+)在特定环境下发生歧化反应,对化学镀铜过程起到催化作用;通过镀层形态和性能测试分析,镀层表面光亮平整,结构致密,与基体结合力强,电阻率为:1.8~2.2μΩ·cm.镀层性能良好,表明可以用亚铜化合物来替代传统化学镀铜的贵金属催化剂.