添加剂N,N-二乙基硫脲,PEG,Cl-对高抗拉电解铜箔电结晶行为的影响

为了揭示在复合添加剂影响下铜电沉积的作用机理,通过线性扫描伏安(LSV)曲线和计时电流(CA)曲线研究了添加剂N,N-二乙基硫脲、聚乙二醇(PEG)和Cl-共存时对铜沉积的影响,同时结合Tafel曲线判断了铜镀层的耐腐蚀性能,并通过SEM表征了铜镀层的微观形貌.试验结果表明:N,N-二乙基硫脲和PEG可以增大阴极极化、成核数密度和镀层的耐蚀性并减小Cu2+的扩散系数,Cl-主要在复合添加剂中起协同作用.10 mg/L N,N-二乙基硫脲、10 mg/L PEG和25 mg/L Cl-协同作用时成核方式始终为瞬时成核,成核数密度达到峰值2.816×106 cm-2,可得到平整细致的电解铜箔.     

添加剂聚乙二醇400对Reline离子液体电沉积Zn过程及镀层组织结构与耐蚀性的影响

目前,鲜见将传统水溶液电镀添加剂用于离子液体电沉积Zn的报道。为了进一步提高锌镀层质量,在含有ZnCl2的氯化胆碱-尿素(Reline)离子液体中添加聚乙二醇400(PEG400),采用循环伏安法研究了PEG400对Zn在Reline-ZnCl2镀液中电沉积过程的影响;并在AM60B镁合金表面脉冲电镀Zn,利用X射线衍射仪(XRD)、扫描电镜(SEM)等分析了脉冲电镀锌层的组织结构和表面形貌,通过极化曲线研究了其耐腐蚀性能。结果表明:Reline-ZnCl2离子液体镀液中加入PEG400添加剂使Zn的还原峰电位负移、峰电流减小,对Zn电沉积产生阻碍作用;PEG400添加剂的加入使脉冲电镀锌层晶面的择优取向发生变化,晶粒显著细化,结构更加致密,镀层耐腐蚀性能提高。     

添加剂丁基黄原酸对碱性羟基乙叉二膦酸体系电沉积铜的影响

过去有关丁基黄原酸添加剂对铜电沉积行为和电极过程影响的研究还不够.采用线性电位扫描(LSV)、计时电流(CA)、交流阻抗和Tafel极化曲线等电化学方法并结合金相显微镜,研究了添加剂丁基黄原酸的浓度对碱性HEDP(羟基乙叉二膦酸)体系镀铜电沉积过程的影响.结果显示:丁基黄原酸在阴极具有一定的吸附能力,对铜沉积有阻化作用,且丁基黄原酸浓度越大,阻化作用越强;铜电沉积的初期行为服从扩散控制和三维连续成核方式生长规律;丁基黄原酸能提高镀液的微观分散能力,使得镀层光滑而平整.     

国外文摘

9703001 氰化物镀Cu的阴极效率——Hatherley P G.TransInstitute of Metal Finishing,1995,73(3):85(英文)测试了氰化物镀Cu溶液的动电位阴极极化曲线,初期沉积的Cu似乎由[Cu(CN)_2]~-释放电荷形成,后由[Cu(CN)_3]~(2-)形成,在极限电流处,沉积过程减缓,阴极效率下降。添加过量的氰化物可促进极限电流时的还原反应,添加碳酸盐和氢氧化物也有类似作用,但碱金属离子降低阴极效率,因此,添加碳酸盐不能提高氰化物镀Cu的阴极效率。9703002 无氰镀Cu工艺——Krishnan R M.Plating and Sur-face Finishing,1995,82(7):56(英文)开发了一种无氰镀Cu工艺,采用该工艺可在碳钢上电沉积结合力良好的镀层,且镀液无公害,不含有毒成分。9703003 Ag-Sn合金电镀——Heraeus W C.欧洲专利,666342.(1995.9.8)(英文)无氰Ag-Sn合金电镀溶液含硝酸银或二氨基络合剂、可溶性Sn(Ⅱ)或Sn(Ⅳ)化合物和巯基链烷羧酸或磺酸,采用以上镀液可沉积出平整,结合力强,含22％～99％Ag的Ag-Sn合金镀层。9703004 氯化物离子在Cu沉积反应中的催化作用——NagyZ.J Electrochem Soc,1995,142(6):87(英文)众所周知,阴离子可促进电极反应,但对微量阴离子所起作用知之甚少,如Cu~(2+)/Cu~+之间的反应明显受镀液中氯化物的影响,而Cu~+/Cu之间的反应     

Cu2O半导体薄膜在酸性条件下的电化学沉积

在酸性溶液中在透明导电玻璃(ITO)基体上电化学沉积Cu2O薄膜.通过实验研究了电沉积工艺条件对电沉积Cu2O薄膜的影响.X射线衍射(XRD)和扫描电镜(SEM)对薄膜的微观结构和表面形貌进行了分析.结果表明,水浴温度较高时,酸性镀液中Ac-HAc共轭缓冲体系的反应速率提高,可以有效抑制铜单质的生长;镀液中铜离子的浓度...     

纳米Si02在电镀锌三价铬钝化中的作用

我国镀锌层三价铬钝化膜的性能仍不完善,为了进一步增加钝化膜的耐腐蚀能力,将纳米SiO2加入到三价铬钝化液中,对电镀锌层进行常温彩色钝化-封闭同步处理。通过中性盐雾试验与电化学极化曲线对钝化膜的抗腐蚀性能进行评价。结果表明：钝化液中纳米SiO2含量为3．5g／L时,钝化液稳定,与三价铬共沉积,产生协同作用,钝化膜光亮,镀...     

复合电沉积法制备Ni-P-W-WC镀层及性能研究

运用电沉积法制备Ni-P-W-WC复合镀层,着重研究了制备工艺和镀层性能.以镀层中碳化钨含量、镀速和镀层外观为指标,探讨了电流密度、电沉积时间、镀液中WC含量、镀液中钨酸钠含量、镀液pH等因素影响规律,确定了复合镀层的最佳工艺条件为:以Ni为阳极、电沉积时间为40 min、镀液中WC含量为14 g/L、镀液中钨酸钠含量为120 g/L、镀液pH为4.0、电流密度是4A/dm2.并用扫描电镜、X-衍射分析仪、阳极极化曲线等手段表征了复合镀层的形貌、结构、耐蚀性、抗氧化性等性能,结果表明,与Ni-P-W复合镀层相比,Ni-P-W-WC复合镀层有良好的综合性能.     

碱性锌镍合金电沉积过程阴极极化的研究

应用恒电流阴极极化技术,研究了以氨水为络合剂的碱性Ｚｎ－Ｎｉ合金镀液体系的电沉积行为,并与单Ｚｎ,单Ｎｉ镀液体系比较,结果表明：当极化电流密度小于转化电流密度ｉｔ（约为０．２６Ａ／ｄｍ＾２）时,Ｚｎ－Ｎｉ体系的极化曲线与单Ｎｉ体系接近,合金电沉积为正常共沉积;而当极化电流密度增大并ｉｔ后,Ｚｎ－Ｎｉ体系极化曲线偏离单Ｎｉ体系,阴极极化率显提高,与单Ｚｎ体系的趋势相同,同时Ｚｎ－Ｎｉ合金电沉积转变     

流动槽滴入法电结晶制备铜钴纳米多层膜

在硼酸镀液体系中采用流动槽滴入法电结晶制得Cu/Co纳米多层膜,通过循环伏安法确定Cu、Co电结晶电位,分别为-0.55V和-1.05V(vs.SCE),通过X射线衍射技术(XRD)和X射线荧光光谱法(XRF)对Cu/Co纳米多层膜的结构、成份进行了分析.并用物性测量系统PPMS测试了Cu/Co多层膜的磁性能,结果表明:电结晶制备的Cu/Co多层膜的矫顽力比较小,仅为34 Oe,适合作巨磁阻磁头材料,其磁电阻随磁场强度的增大而减小,且约在3000 Oe时磁电阻趋于饱和,此时的巨磁阻效应GMR值达到了14%.     

稀土在氯化物体系电沉积锌-铁合金中的作用

为了研究稀土在电沉积锌-铁合金中对镀层和镀液的作用,通过在镀液中添加LaCl3后,对镀层组分、厚度、耐蚀性的改变,镀液稳定性、分散力以及阴极极化作用的影响进行了研究.结果发现,稀土的加入有利于提高镀液稳定性、分散能力和减薄镀层,使锌-铁合金镀层的耐蚀性在中性5%NaCl溶液中有较大提高.研究表明,稀土盐的加入能改善镀液性能,改变镀层成分和锌-铁合金电沉积的阴极极化行为,同时提高镀层的耐腐蚀性.     

A SERS study of the galvanostatic sequence used for the electrochemical deposition of copper from baths employed in the fabrication of interconnects

This paper reports the first study carried out by surface-enhanced Raman spectroscopy (SERS) during the galvanostatic electrodeposition (ECD) of copper from an acidic sulphate solution, in the presence of polyethylene glycol (PEG), bis-(3-sulfopropyl)-disulfide Na salt (SPS), benzyl–phenyl modified polyethyleneimine (BPPEI) and chloride ions. The analysis of SERS spectra recorded during electrodeposition allowed to get an insight into the complex interfacial behaviour of the organic blend, in terms of co-adsorption and reactivity. At open-circuit (OC), the additives co-adsorb on the copper cathode. Upon increasing the cathodic polarization, progressive SPS-scavenging action of PEG was observed. BPPEI is adsorbed in the entire process window and cathodic reaction products of PEG were identified. The joint action of the organic additives yields a continuous deposit with crystallites of submicron dimensions, as revealed by Scanning electron microscopy (SEM).     

The corrosion behavior of copper in acid soil during soil acidification by simulated acid rain

The corrosion behaviors of copper in acid soil during soil acidification by simulated acid rain (SAR) were studied by means of polarization curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results indicated that the SAR increased the corrosion rate of the copper in the acidic soil. The corrosion rate of the copper increased with decreasing pH value of SAR. Corrosive characteristics of the soil obviously increased because of the leaching of the acid rain. For the leaching of the distilled water, the corrosion rate of the copper decreased. EIS of copper was a capacitive loop in the early stage of corrosion. After 60 days exposure, EIS consisted of two capacitive arcs for copper in the acidic soil leached with SAR, the control step for corrosion of copper was charge transfer process. For the distilled water, EIS consisted of a capacitive loop at higher frequency and a Warburg impedance at lower frequency, and the control step for corrosion of copper was diffusion process.     

酞菁染料与氯离子协同效应在酸性镀铜中的作用

采用旋转圆盘电极和交流阻抗方法研究酞菁染料（PC）及其与氯离子协同效应对酸性镀铜电沉积过程的影响，通过选择不同浓度的酞菁染料，研究它们在不同转速下的阴极极化行为和交流阻抗图谱，对其在电极表面的成膜状态作了深入研究。极化的电位从自然电位到－0．6V（相对SCUE）。结果表明，PC在酸铜电镀中所起的作用更多依赖于其在表面形成吸附膜的结构，而非单纯的电荷吸引。     

表面活性剂PEG6000对二元络合体系化学沉积铜的影响

研究了表面活性剂聚乙二醇6000对乙二胺四乙酸(EDTA)/四羟丙基乙二胺(THPED)二元络合体系化学镀铜的过程和化学镀铜表面结构的影响。混合电位-时间测试结果表明,化学沉积过程分为三个区：诱发区、过渡区和稳定区。PEG6000使体系的混合电位负移趋势放缓,与表面活性剂在铜表面的吸附阻滞了对带电荷离子的吸附有关。线性扫描测试结果表明,阴极还原反应为控制步骤,PEG6000的吸附减缓了阴极还原反应,还原峰电流密度下降了约40%;铜化学沉积速率随着PEG6000浓度的提高呈线性下降趋势。SEM、EDS和XRD表征结果表明,化学镀铜的纯度较高,加入PEG6000使镀层呈现出明显的(220)晶面择优取向,且晶粒尺寸由77.7 nm减小到50.0 nm,有细化晶粒的作用。     

铜铁界面含氧层对镀层结合强度的影响

镀层与基体界面间含氧层的存在,影响电镀层与基体之间金属键的形成,进而影响镀层的结合强度.用氰化物和焦磷酸盐两种工艺在铁片上镀铜,对镀层进行恒电流极化,并以氩离子深度刻蚀和X射线光电子能谱相结合的方法进行检测.电沉积初始电位-时间曲线显示,两种镀铜工艺,结合强度好的出现了基体表面的还原活化电位平阶,结合强度差的焦酸盐镀铜未出现活化就发生了金属的电沉积,而且铜镀层与基体界面含氧量有增高的现象.铜镀层与铁基底界面间含氧层的存在是影响镀层结合强度的主要原因.通过控制金属电沉积初始电位可提高镀层的结合强度.     

Fabrication of Au/ZnO Schottky nanodiode using mesoporous silica film as template

Au/ZnO Schottky nanodiode is prepared by two-step electrodeposition, using mesoporous silica (MPS) film as template. Nano-ZnO is firstly deposited in the pores of MPS film, which achieves enhanced conductivity and enables continued electrodeposition of Au to form an Au/ZnO Schottky nanodiode. Current-voltage (I-V) curves of Au/ZnO nanodiode are recorded under a switched UV-light with the wavelength of 365 nm. The characteristic I-V curves show rectifying behavior in the dark, and present more linear Ohmic response upon UV exposure, which might be caused by the lowered Schottky barrier height and narrowered Schottky barrier width. In addition, fast increased forward-current and lowered breakdown voltage are observed from I-V curves of Au/ZnO Schottky nanodiode. The ideality factor of the Au/ZnO Schottky diode is determined to be approximately 8. These results suggest a different photocurrent-generation process, and provide experimental support to the model proposed in ultrasmall Schottky diodes.     

Photosensitive self-assembled membrane of cysteine against copper corrosion

Complex self-assembled membrane (SAM) was prepared by modifying the adsorption of cysteine with fluorescent reagent sodium 1-naphthylamine diacetate (NADA) on copper surface. The SAM has a fluorescence emission at 430 nm. Its protective effects against copper corrosion were investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in 0.5 M NaCl solution. It suppresses cathodic current densities and shifts the corrosion potential toward more positive values. The variation of the fluorescence intensity is correlated to that of the impedance resistance. The fluorescence detection provides a potential monitoring method for the protection of the SAM on copper surface.     

电沉积与铁基体电位活化的增强拉曼光谱研究

为探讨电沉积初始过程对电镀层结合强度的影响,采用循环伏安法和表面增强拉曼(SERS)光谱研究了光亮铁电极在5%KCl溶液中表面氧化物随电位负移的还原过程,并应用循环伏安法和恒电流电位-时间法研究了氰化物镀铜体系铁基体的电位活化现象和电沉积初始过程.结果表明,在电位-0.9 V时,特征波数为424 cm-1和499 cm-1的Fe3O4谱峰消失,电位-1.2 V时,特征波数671 cm-1的FeO、谱峰明显降低,说明Fe3O4和FeO在不同电位下依次实现还原过程.循环伏安曲线在-0.9 V及-1.2 V附近也依次出现了铁氧化物的还原电流平阶.在氰化物镀液中,铜的析出电位(约-1.4 V)负于铁表面氧化物的还原电位,电极过程首先实现铁表面氧化物的还原,随后铜沉积在活化的铁基体上.     

Studies of the corrosion inhibition of copper in sodium chloride solutions using chemical and electrochemical measurements

The inhibiting effects of 2-mercapto-4-amino-5-nitroso-6-hydroxy pyrimidine (MAP) at various concentrations on the copper corrosion in 3.5% NaCl solutions at 25 °C are examined. The inhibiting efficiency of MAP is evaluated from weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and electrochemical frequency modulation (EFM) measurements. Experimental investigations showed that MAP reduces markedly the copper corrosion in 3.5% NaCl solutions, and this reduction in corrosion rates enhances with increasing concentration of this compound. The results obtained from the different corrosion evaluation techniques are in good agreement. Polarization curves indicate that MAP is a mixed-type inhibitor. The results of EIS indicate that the value of CPEs tends to decrease and both charge transfer resistance and inhibition efficiency tend to increase by increasing the inhibitor concentration. EFM can be used as a rapid and non-destructive technique for corrosion rate measurements without prior knowledge of Tafel constants.     

Electrodeposition of Zirconia Particles in a Copper Matrix

Electrochemical codeposition is one of the most important methods of providing composites with metallic or nonmetallic compounds as a second phase, in a metallic matrix or nonmetallic matrix. Composite coatings can be prepared by electrodeposition from an electrolytic solution containing a suspension of insoluble ZrO₂ particles. Interesting applications have been developed for wear resistance, dry lubrication, anticorrosion, dispersion hardening, and electrocatalysis. The aim of the present study is to obtain a better understanding of the effects of the dispersed particles on the mechanism of copper electrocrystallization and on the incorporation rate of dispersed phase in the deposit. Cathodic polarization curves in electrolytes with and without dispersed particles were plotted to identify their influence in the process of metal electrodeposition. The effect of the operating parameters (current density, concentration of the dispersed phase in the electrolyte) on the concentration of the dispersed phase in the composite layer is described by means of simple mathematical equations.