Kinetics of electroless Ni-Cu-P deposits on silicon in a basic hypophosphite-type bath

Eleetroless Ni-Cu-P deposits were deposited on the Si substrate in a basic hypophosphite-type plating bath.The effects ofpH value and the metal source composition, Ni and Cu, in the plating bath on the kinetics of the Ni-Cu-P deposition were studied.The electroless Ni-Cu-P deposits were characterized by a scanning electron microscope, a transmission electron microscope, an en-ergy dispersive X-ray spectroscope, and an X-ray diffractometer.The results showed that the pH value of the plating bath had no ob- vious effect on the morphology and composition of electroless Ni-Cu-P deposits.However, the composition of the metal source, Ni and Cu, in the plating bath had great effect on the kinetics of electroless Ni-Cu-P deposition.     

兼容性Cu2+溶液改性EP基材催化铜导电线路沉积

印制电路板(PCB)基材预设位置活化是选择性化学镀铜法制作导电线路的关键工艺。以乙酸铜为催化剂前驱体、硫脲为络合剂、双酚A二缩水甘油醚为环氧树脂(EP)预聚物、试剂593为固化剂和丙二醇甲醚为溶剂,设计出一种基于EP兼容的Cu2+溶液,借助喷墨打印机把兼容性Cu2+溶液印刷在EP基材表面,采用选择性化学镀铜法加成制备了铜导电线路。基于量子化学密度泛函理论,模拟兼容性Cu2+溶液中硫脲分子与Cu2+之间的络合反应,利用红外光谱和拉曼光谱对兼容性Cu2+溶液中特殊官能团进行表征。结果表明:铜线路中晶粒结晶度良好且堆积致密,其电阻率低至2.62×10?6 Ω·cm;在改性层的帮助下,铜线路与EP基材之间的结合力达到5B级别。因此,EP基材兼容性改性催化铜导电线路沉积具有工艺简单、经济环保的优点,这对其他常用树脂基材兼容性改性加成制备PCB具有一定的参考价值。     

Electroless plating of carbon nanotubes and their millimeter-wave absorbing properties

A method of electroless plating was utilized to deposit Cu, Ni, Co, Ag on the surface of carbon nanotubes (CNTs) respectively, in order to prepare millimeter-wave absorbing materials. Field emission scanning electron microscope (FE-SEM) and energy dispersive spectrometer (EDS) were used to observe morphologies and chemical compositions of the samples respectively. Millimeter-wave radiometer imaging detection was employed to measure the absorbing properties of the samples. FE-SEM and EDS results demonstrate the effectiveness of successful metal deposition. The results of millimeter-wave radiometer imaging detection reveal that the millimeter-wave absorbing properties of electroless-silver plating are better than other kinds of samples.     

Preparation of copper-coated fine molybdenum powders with electroless technique

The molybdenum powders with average particle size of 3 μm were coated with copper by electroless plating. The influence of pretreatment,solution composition and plating conditions on electroless copper plating was studied. The copper-coated molybdenum powders were examined by SEM and XRD. Results indicate that a series of optimization methods is used to add activated sites before electroless copper plating. Taking TEA and EDTA as chief and assistant complex agents respectively,2,2’-bipyridyl and PEG as double stabilizers,the Mo powders are coated with copper successfully with little Cu2O contained,at the same time,Mo-Cu composite powders with copper content of 15-85 wt% can be obtained. The optimal values of pH,temperature and HCHO concentration are 12-13,60-65 ℃ and 22-26 mL/L,respectively.     

化学镀法制备钴包覆碳化硅复合粉末的研究

采用化学镀法制备钴包覆碳化硅复合粉末,通过研究化学镀过程中钴盐浓度、还原剂浓度、络合剂浓度、缓冲剂浓度、温度以及pH值等因素对沉积速率的影响规律,得到化学镀钴的优化条件。利用XRD、SEM和EDAX等测试手段对该复合粉末的组分及形貌进行了表征。实验和表征结果表明,当硫酸钴浓度为30～50g/L,次磷酸钠浓度为40g/L,柠檬酸钠浓度为60～70g/L,控制温度为50～70℃以及调节pH值等于8时,镀层沉积速度较快,所得粉体表面被钴均匀包覆。     

Study on the characterization and technology of Cu thin-film temperature sensor fabricated on aluminum alloy

In the present study,anodic films on aluminium alloy was used as the dielectric layer for Cu thinfilm temperature sensor,and then Cu film was deposited by unbalanced magnetron sputtering ion plating as the sensitive layer.Microstructure and surface morphologies of Cu film were investigated by optical microscope（OM）,atomic force microscope（AFM） and scanning electron microscope（SEM）.Electrical properties of Cu thin-film temperature sensor were tested by four-point probe technique and Digit Multimeter.The results showed that the surface roughness of anodic films can be reduced from Ra 58.096 nm to Ra 16.335 nm by proper polishing.Continual Cu stripes can be obtained both on polished anodic alumina film and smooth alumina wafer by etching after Cu film annealing.The resistivity of Cu films before and after 300 ℃ as well as 400 ℃ annealing are 12.48 mΩ·cm,5.48 mΩ·cm and 4.83 mΩ·cm,respectively.The resistances of Cu thin-film temperature sensor in 70 ℃ and 0 ℃ are 946.5 Ω and 761.15 Ω respectively.The temperature coefficient of resistivity（TCR） of the sensor is 3479 × 10^{- 6} /℃.     

Fabrication of W@Cu composite powders by direct electroless plating using a dripping method

A direct electroless copper (Cu) coating on tungsten powders method requiring no surface treatment or stabilizing agent and using glyoxylic acid (C₂H₂O₃) as a reducing agent was reported. The effects of copper sulfate concentration and the pH of the plating solution on the properties of the prepared W@Cu composite powders were assessed. The content of Cu in the composite powders was controlled by adjusting the concentration of copper sulfate in the electroless plating solution. A uniform, dense, and consistent Cu coating was obtained under the established optimum conditions (flow rate of C₂H₂O₃ = 5.01 mL/min, solution pH = 12.25 and reaction temperature 45.35 °C) by using central composite design method. In addition, the crystalline Cu coating was evenly dispersed within the W@Cu composite powders and Cu element in the coating existed as Cu0. The formation mechanism for the W@Cu composite powders by electroless plating in the absence of surface treatment and stabilizing agent was also proposed.     

二维纳米结构——氧化铋纳米片的制备与表征

利用物理气相沉积法,在氩气和氧气保护下将氧化铋粉末在水平管式炉中常压加热至1050℃,然后降温沉积,在硅衬底上得到了大量具有规则矩形外形的二维纳米结构——片状氧化铋.纳米片的长约1200nm,宽约300nm,厚约10～15nm.采用扫描电镜（SEM）,X-ray能谱仪（EDS）、高分辨透射电镜(HRTEM)等测试手段分析了样品的形貌、成分及微结构.研究分析了衬底放置方式对产物沉积量的影响.     

Mechanism and Microstructure of Electroless Ni-Fe-P Plating on CNTs

Electroless Ni-Fe-P alloy plating on the surface of CNTs was carded out with a bath using citrate salt and lactic acid as complex agents. We proposed a chemical reaction mechanism. The morphology, structure and chemical composition of the Ni-Fe-P/CNTs were studied with the aid of a scanning electronic microscope （SEM）, X-ray diffraction （XRD） and an energy-dispersive X-ray spectral analysis （EDS）. The results show that through a correct pre-treatment and electroless plating, Ni-Fe-P/CNTs composite particles can be obtained. The optimum electroless plating parameters of 35-42℃ and pH of 8.5-9.7 were achieved. The as-plated Ni-Fe-P alloy is amorphous. After a heat treatment at 500℃ for 90 min in H2, the coating is transformed into crystalloid Ni3E Fe2NiP and （Fe,Ni）3R The Ni-Fe-P alloy coating on the surface of CNTs is smooth and unique. The amount of Ni on the surface （mass fraction） of the Ni-Fe-P/CNTs composite particles is 29.13%, that of Fe 3.19% and that of P 2.28%.     

碳酸钙粉体无钯活化化学镀银研究

采用无钯活化粉体化学镀技术制备了银包碳酸钙导电粉体.探讨了表面处理和PH值对沉积效果的影响,以及复合粒子的结合强度.通过扫描电镜(SEM),X射线能量色散谱仪(EDS)和X射线衍射(XRD)对复合粉体进行表面形貌分析和成分测试.结果表明:碳酸钙粉体经WD-50表面处理后,生成的银粒子粒径较小,对碳酸钙粒子的包覆均匀致密.随着镀液pH值的升高,银的析出量增大,粉体表观颜色变浅.调节镀液pH至13.0,得到了镀层结合强度高的银包碳酸钙复合粉体.     

酸性镀液铝合金表面沉积Ni-Mo-P三元合金非晶镀层

采用酸性化学镀液在铝合金表面沉积Ni-Mo-P三元合金非晶镀层。利用透射电镜（TEM）、场发射扫描电镜（FESEM）、X射线衍射分析（XRD）、能谱（EDS）等现代分析手段,对镀层显微结构进行了表征,探讨了钼酸钠浓度和热处理对镀层纳米压痕硬度的影响。结果表明,镀态下,化学镀Ni-Mo-P三元合金镀层为致密非晶态镀层,镀层中Mo元素分布均匀,镀层与基体结合良好。热处理可促使非晶镀层晶化,产生Ni和Ni3P晶相,获得了纳米压痕硬度为15.12 GPa的最大值。     

Enhanced Corrosion and Wear Resistances of Zr-based Alloy Induced by Amorphous/Nanocrystalline Coating

To improve corrosion and wear resistances of the Zirconium(Zr) based alloys which are widely applied in nuclear reactors and chemical corrosion-resistant equipment, a new surface modification scheme was designed to deposit a Zr_(75)Cu_(25) coating on Zr substrate by using magnetron sputtering technique. The microstructure and the phase composition were characterized by scanning electron microscope, transmission electron microscope, and X-ray diffraction measurements. The tribological properties and the corrosion resistance were investigated by performing reciprocating tribo-tester and electrochemical tests, respectively.It is found that the Zr_(75)Cu_(25) coating is made up of a mixture of amorphous and a-(Zr) nanocrystalline phases.The nanocrystalline particles with a size of 5-10 nm are homogenously dispersed in the amorphous matrix.The Zr_(75)Cu_(25) coating shows excellent tribological properties, due to the dispersion strengthen caused by the homogeneous distribution of a-(Zr) nano-size particles among the amorphous matrix. In addition, it is revealed that the Zr_(75)Cu_(25) coating makes the Zr substrate exhibit excellent corrosion resistance, due to the robust passive film with a compact structure of the amorphous/nanocrystalline mixture.     

多孔硅还原铜纳米复合薄膜的微结构研究

利用扫描电镜(SEM)、XRD等分析手段对比研究了铁钝化多孔硅在沉积前与沉积后的结构变化特点以及沉积时间对所沉积的铜薄膜结构的影响.在浸渍一定时间后,铜/铁钝化多孔硅纳米复合薄膜继承了新鲜制备的铁钝化多孔硅的结构特点,同时,随着反应时间的延长,铜的沉积量逐渐增加,铜纳米颗粒的平均晶粒尺寸逐渐长大.     

湿化学法制备纳米AgSnO2复合粉末的研究

将银氨溶液滴加到含纳米SnO2颗粒的甲醛溶液中进行超声波化学镀银。粒度检测和扫描电镜观察结果表明，采用分散性良好的纳米SnO2浆料，可以获得平均粒度为140 nm的AgSnO2复合粉末；而采用纳米SnO2粉末，所得复合粉末的粒度较大，原因是粉末之间存在严重的团聚。将氢氧化钠加入甲醛溶液进行镀覆，提高了Ag的形核能力，可以得到平均粒度为75 nm的复合粉末。     

玻璃表面化学镀纳米铜膜

利用化学镀铜工艺,以十二烷基苯磺酸钠(SDBS)作为镀液添加剂,在未经刻蚀的玻璃表面制备了纳米铜膜。采用FESEM、SEM和XRD等技术对铜膜表面、断面形貌及晶体结构进行了表征。结果表明,铜膜内团簇尺寸非常细小,晶粒尺寸约为15.5~28.3 nm,且存在较强的〈111〉织构。采用四探针法测量铜膜的电阻率,并讨论了电阻率随沉积时间增加而逐渐下降的原因。     

Research on Surface Modification of 96 Al2O3 by Ni Ion Implantation

A matrix of 96 Al2O3 ceramics was implanted with Ni ion of different dosages and energies using a MEVVA implanter. Then metallic structures of copper were made on the implanted ceramics, by using selective electroless copper plating. In addition, the characteristics and microstructure of the implanted layer were studied by using the SEM, RBS and XPS. The results show that： 1） the implanted Ni exits as Ni^2, Ni^2＋, and Ni^3＋ in the surface of Al2O3 and metal Ni particles precipitate on ceramics during implantation; 2） the concentration of Ni submits to the Gauss distribution along the direction of implantation on the surface of Al2O3 and high Ni concentration on the surface can be obtained if the Ni is implanted with low energy and a high dosage and 3） Ni ion implantation can activate the surface of Al2O3 and induce electroless copper plating on the ceramics.     

超微金刚石对Ni-P化学复合镀层性能的影响

为改善Ni-P化学镀层的性能,采用化学复合镀的方法在镀层中添加了爆轰合成超微金刚石(Ul-trafine Diamond,UFD).研究了复合镀层的形成机理及镀液中UFD含量对复合镀层显微硬度及耐磨性的影响规律.实验用UFD众数粒径为114.6 nm.镀层显微硬度采用国产71型显微硬度仪进行检测,耐磨性采用国产MM200型磨损试验机进行检测.结果表明:随着镀液中UFD的加入,Ni-P合金粒子会以UFD颗粒为核心形成硬度较高的"包覆球"."包覆球"沉积到镀件表面形成复合镀层.复合镀层的显微硬度及耐磨性均随镀液中UFD含量的不同呈规律性变化.与Ni-P化学镀层相比,当镀液中UFD含量为0.8 g/L时,复合镀层显微硬度可提高0.6倍;当镀液中UFD含量为1.0 g/L时,复合镀层耐磨性可提高4.8倍.     

Fabrication of Stable Superhydrophobic Cupric Hydroxide Surface with Hierarchical Structure on Copper Substrate

Cupric hydroxide films with a new hierarchical architecture consisting of beautiful nanotubes and nanoflowers were directly fabricated on copper substrate via a solution-immersion process at a constant temperature of 23?℃. Stable superhydrophobic Cu(OH)₂ surface was obtained after Cu(OH)₂ films were modified with hydrolyzed 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane (C₈H₄Cl₃F₁₃Si, FOTMS). The surface morphology and composition of the film were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. Result shows that the surface of Cu(OH)₂ films directly grown on copper substrate was hydrophilic, whereas the modified Cu(OH)₂ films exhibited the superhydrophobicity with a water contact angle (CA) of about 160.8°, as well as a small sliding angle (SA) of about 1°. The special hierarchical structure, along with the slow surface energy leads to the high superhydrophobicity of the surface.     

NaTaO_3光催化剂的溶剂热法制备及其性能研究

采用溶剂热法在温和的条件下制备粒径在200~300 nm、结晶较好的NaTaO3纳米晶体。并借助X射线衍射、发射-扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)等手段分别对其晶相、微观形貌进行表征。结果表明:水热体系140℃即可得到纯的NaTaO3晶体,升高反应温度有利于钙钛矿结构纳米NaTaO3晶体的生长;乙醇体系不能得到NaTaO3晶体,而乙醇/水混合体系在120℃可得到纯NaTaO3。用5 mg.L-1藏红T溶液作为降解液进行光催化降解实验,结果表明所得样品有较高的催化活性。     

单晶硅表面磁控溅射铜栅极

晶硅太阳能电池表面的导电栅极主要用于输出电能,若其与基体间的附着力较差,将会极大地降低电池元件的稳定性和使用寿命,而与其他制备方法相比,物理气相沉积法具有可控性好、成本低等优势. 为了继承物理气相沉积法的相关优势,同时能够使铜栅极与基片之间具有良好的附着力,利用磁控溅射法在单晶硅上进行铜栅极的制备实验,研究了磁控溅射过程中溅射功率和工作气压等参数对最终制得的铜栅极附着力的影响. 采用超声震荡加强实验检测铜栅极的附着力,使用金相显微镜观察铜栅极的整体形貌及断线率,通过扫描电子显微镜观察铜膜的表面形貌. 结果表明在溅射功率为180 W,工作气压为0.8 Pa的条件下制备的铜栅极线宽更为均匀,且进行加强实验后断线率为0.