CO2-3对羟基乙叉二膦酸镀铜液的影响

研究羟基乙叉二膦酸(HEDPA)镀铜液中CO32-含量对电沉积时阴、阳极过程及镀层的择优取向的影响.通过分析阴、阳极的动电位极化曲线,发现镀液中逐渐加入的CO32-提高了阴极的极化,使电结晶晶粒细化,直至达到稳定;同时促进了铜阳极的溶解.而X射线衍射(XRD)结果表明,铜镀层的晶面择优取向从(222)逐渐向(111)转变.通过镀液中固体络合物的红外光谱分析表明,CO32-的加入以第二配体的方式进入该镀液的放电络合离子结构中,参与Cu2+的络合,形成更稳定的络合物,从而导致铜沉积电位负移,镀层(111)晶面取向增强.     

CO3^2-对羟基乙叉二膦酸镀铜液的影响

研究羟基乙叉二膦酸（HEDPA）镀铜液中CO3^2-含量对电沉积时阴、阳极过程及镀层的择优取向的影响.通过分析阴、阳极的动电位极化曲线,发现镀液中逐渐加入的CO23-提高了阴极的极化,使电结晶晶粒细化,直至达到稳定;同时促进了铜阳极的溶解.而X射线衍射（XRD）结果表明,铜镀层的晶面择优取向从（222）逐渐向（111）转变.通过镀液中固体络合物的红外光谱分析表明,CO3^2-的加入以第二配体的方式进入该镀液的放电络合离子结构中,参与Cu2＋的络合,形成更稳定的络合物,从而导致铜沉积电位负移,镀层（111）晶面取向增强.     

高择优取向Cu电沉积层的XRD研究

采用电化学和XRD方法在CuSO4 +H2 SO4 电解液中获得Cu电沉积层并研究其结构 .结果表明 ,在 4 .0A/dm2 和 15 .0A/dm2 电流密度下可分别获得 (2 2 0 )和 (111)晶面高择优取向Cu镀层 ;Cu镀层晶面织构度随厚度提高而增大 ,获得 (111)晶面高择优Cu镀层的厚度约是 (2 2 0 )晶面的 7倍 ,说明Cu(2 2 0 )晶面比 (111)晶面是更易保留的晶面 ,且低电流密度下铜的电结晶更容易受电沉积条件控制 ;较高的沉积电流密度有利于晶核的形成 ;Cu镀层存在晶格畸变和晶胞参数的涨大     

2,2′-联吡啶在化学镀铜中的作用研究

研究了以次磷酸钠作还原剂的化学镀铜体系,添加剂2,2′-联吡啶对化学镀铜沉积速率、次磷酸钠阳极氧化和铜离子阴极还原、以及镀层形貌、结构和组分存在状态的影响.结果表明,2,2′-联吡啶对化学沉积起阻化作用.电化学线性伏安扫描实验显示,镀液中加入2,2′-联吡啶,次磷酸钠的氧化峰电势有所负移,但峰电流减小;铜离子的还原峰电势负移,但峰电流逐渐增大.扫描电子显微镜(SEM)、能量色散谱(EDS)、X射线衍射(XRD)及X射线光电子能谱(XPS)等实验分别表明,添加剂使镀层致密和光亮、镍含量降低;镀层为Cu-Ni合金,呈面心立方结构,无明显晶面择优取向现象;镀层中铜和镍以金属态存在,磷的质量含量小于0.05%.     

氟硼酸镀液二氧化铅电沉积

研究了在氟硼酸或其掺杂镀液中于Pt基底电沉积PbO2镀层的电化学和结构性质.循环伏安测试、XRD分析和SEM形貌观察表明,BF4-可提高二氧化铅电沉积速率;电沉积的PbO2晶型为β-PbO2;F-、Fe3+共掺杂影响晶体生长的择优取向及镀层形貌,电沉积的FB/F-Fe-PbO2镀层整齐致密;电沉积过程增大电流密度可改变生长晶面取向.     

CO2-3对羟基乙叉二膦酸体系铜电结晶的影响

采用循环伏安和计时安培法研究了羟基乙叉膦酸(HEDPA)镀铜液中铜在玻碳电极上电结晶的初期行为.结果表明:羟基乙叉二膦酸(HEDPA)镀铜体系中,铜的电沉积过程经历了晶核形成过程;当溶液中不含CO32-时,其电结晶按连续三维成核方式进行,而随着CO32-的逐渐加入,使得铜电结晶按瞬时三维成核方式过渡;成核数密度都随着电位的提高而增加.这可能是CO32-以第二配体形式进入HEDPA和CU2+构成的络合结构,从而形成更稳定的络合物吸附在电极表面所致.     

纳米Al_2O_3颗粒对镍电结晶过程的影响

借助循环伏安(CV)和计时安培(CA)研究了在不同电位下,纳米Al2O3微粒对镍由硫酸盐混合溶液在铜基底上电结晶沉积的影响.结果表明,Ni-Al2O3镀液体系电沉积的起始电位约为-740 mV.随着阶跃电位负移,Ni-Al2O3镀液体系电沉积成核时间tm逐渐缩短.与纯Ni镀液体系电沉积的tm相比,在-740~-830mV较低阶跃电位下,Ni-Al2O3镀液体系电沉积的成核时间tm明显缩短,表明Al2O3微粒有助于镍的电结晶成核.在-890 mV阶跃电位下,Ni-Al2O3镀液体系电沉积初始阶段的成核过程满足Scharifker-Hills三维瞬时成核模型.     

2，2＇-联吡啶在化学镀铜中的作用研究

研究了以次磷酸钠作还原剂的化学镀铜体系，添加剂2，2＇-联吡啶对化学镀铜沉积速率、次磷酸钠阳极氧化和铜离子阴极还原、以及镀层形貌、结构和组分存在状态的影响．结果表明，2，2＇-联吡啶对化学沉积起阻化作用．电化学线性伏安扫描实验显示，镀液中加入2，2＇-联吡啶，次磷酸钠的氧化峰电势有所负移，但峰电流减小；铜离子的还原峰电势负移，但峰电流逐渐增大．扫描电子显微镜（SEM）、能量色散谱（EDS）、X射线衍射（XRD）及X射线光电子能谱（XPS）等实验分别表明，添加剂使镀层致密和光亮、镍含量降低；镀层为Cu-Ni合金，呈面心立方结构，无明显晶面择优取向现象；镀层中铜和镍以金属态存在，磷的质量含量小于0．05％．     

CO32-对羟基乙叉二膦酸体系铜电结晶的影响

采用循环伏安和计时安培法研究了羟基乙叉二膦酸(HEDPA)镀铜液中铜在玻碳电极上电结晶的初期行为。结果表明：羟基乙叉二膦酸(HEDPA)镀铜体系中,铜的电沉积过程经历了晶核形成过程;当溶液中不含CO32-时,其电结晶按连续三维成核方式进行,而CO32-的加入,使得铜电结晶按瞬时三维成核方式进行;成核数密度都随着电位的提高而增加。这可能是CO32- -以第二配体形式进入HEDPA和Cu2+构成的络合结构,从而形成更稳定的络合物吸附在电极表面所致。     

三乙醇胺对羟基亚乙基二膦酸镀铜液的影响研究

研究羟基亚乙基二膦酸(HEDPA)镀铜液中三乙醇胺(TEA)对铜还原和氧化过程的影响. 用Hull Cell测试阴极电流密度分布, 通过电位扫描、循环伏安和交流阻抗研究铜沉积的电化学行为, 通过镀液的吸光度测试和固体配合物的红外光谱分析推断配位化合物的形式. 结果表明: TEA的加入能够扩大HEDPA镀铜体系的阴极允许电流密度, 对铜电沉积有阻化作用, 促进铜阳极溶解, 并可抑制氢气的析出|随着溶液中TEA浓度增加, 在玻碳电极上发生的铜还原过程由电化学控制逐渐转变为扩散控制, 可获得结晶细小、表面平整的致密铜镀层. TEA的加入, 主要是在HEDPA镀铜体系中形成CuTEA(OH)₂配位化合物, 并吸附在电极表面而影响电化学反应.     

Ni-Mo合金电沉积层织构及形成机理

在组成为：０．２２ｍｏｌ／Ｌ硫酸镍、０．０６ｍｏｌ／Ｌ钼酸钠和０．３ｍｏｌ／Ｌ柠檬酸钠的溶液,于纯铜片上采用恒电流沉积,所得Ｎｉ－Ｍｏ合金沉积层经Ｘ射线衍射测定,结果表明在温度为２５℃～５０℃,电流密度为１０ｍＡ·ｃｍ－２～３０ｍＡ·ｃｍ－２范围,Ｎｉ－Ｍｏ合金沉积层表现为（１１１）择优取向．循环伏安和电位阶跃实验表明镍钼合金电结晶过程按照连续成核和三维生长方式进行．Ｎｉ－Ｍｏ合金电沉积过程的电化学交流阻抗谱表明Ｎｉ－Ｍｏ共沉积过程经历了吸附中间产物步骤,由于吸附态物种氢氧化镍和钼的氧化物将阻化晶粒（１１１）晶面的生长,从而使镍钼沉积层表现为（１１１）择优取向．     

Electrochemical and PM-IRRAS studies of the effect of the static electric field on the structure of the DMPC bilayer supported at a Au(111) electrode surface

Differential capacity, charge density measurements, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) were employed to study the fusion of small unilamellar vesicles of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) on a Au(111) electrode surface. The differential capacity and charge density data showed that the vesicles fuse onto the gold surface at charge densities between -10 microC/cm(2) < sigma(M) < 10 microC/cm(2) to form a bilayer. When sigma(M) < -10 microC/cm(2), the film is detached from the surface but it remains in close proximity to the surface. PM-IRRAS experiments provided IR spectra for the bilayer in the adsorbed and the desorbed state. Ab initio normal coordinate calculations were performed to assist interpretation of the IR spectra. The IR bands were analyzed quantitatively, and this analysis provided information concerning the conformation and orientation of the acyl chains and the polar head region of the DMPC molecule. The orientation of the chains, hydration, and conformation of the headgroup of the DMPC molecule strongly depend on the electrode potential.     

CO adsorption and reaction on clean and oxygen-covered Au(211) surfaces

We have used primarily temperature-programmed desorption (TPD) and infrared reflection-absorption spectroscopy (IRAS) to investigate CO adsorption on a Au(211) stepped single-crystal surface. The Au(211) surface can be described as a step-terrace structure consisting of three-atom-wide terraces of (111) orientation and a monatomic step with a (100) orientation, or 3(111) x (100) in microfacet notation. CO was only weakly adsorbed but was more strongly bound at step sites (12 kcal mol(-1)) than at terrace sites (6.5-9 kcal mol(-1)). The sticking coefficient of CO on the Au(211) surface was also higher ( approximately 5x) during occupation of step sites compared to populating terrace sites at higher coverages. The nu(CO) stretching band energy in IRAS spectra indicated that CO was adsorbed at atop sites at all coverages and conditions. A small red shift of nu(CO) from 2126 to 2112 cm(-1) occurred with increasing CO coverage on the surface. We conclude that the presence of these particular step sites at the Au(211) surface imparts stronger CO bonding and a higher reactivity than on the flat Au(111) surface, but these changes are not remarkable compared to chemistry on other more reactive crystal planes or other stepped Au surfaces. Thus, it is unlikely that the presence or absence of this particular crystal plane alone at the surface of supported Au nanoparticles has much to do with the remarkable properties of highly active Au catalysts.     

IR chemiluminescence probe of the vibrational energy distribution of CO2 formed during steady-state CO oxidation on Pt(111) and Pt(110) surfaces

The infrared (IR) chemiluminescence spectra of CO2 were measured during the steady-state CO + O2 reaction over Pt(110) and Pt(111) surfaces. Analysis of the IR emission spectra indicates that the bending vibrational temperature (TVB), as well as the antisymmetric vibrational temperature (TVAS), was higher on Pt(110) than on Pt(111). On the Pt(110) surface, the highly excited bending vibrational mode compared to the antisymmetric vibrational mode was observed under reaction conditions at low CO coverage (theta(CO) < 0.2) or at high surface temperatures (TS > or = 700 K). This can be related to the activated complex of CO2 formation in a more bent form on the inclined (111) terraces of the Pt(110)(1 x 2) structure. On the other hand, at high CO coverage (theta(CO) > 0.2) or at low surface temperatures (TS < 650 K), TVAS was higher than TVB, which can be caused by the reconstruction of the Pt(110)(1 x 2) surface to the (1 x 1) form with high CO coverage.     

Structure of activated complex of CO2 formation in a CO + O2 reaction on Pd(110) and Pd(111)

Examinations of CO2 formed during steady-state CO oxidation reactions were performed using infrared (IR) chemiluminescence. The CO2 was formed using a molecular-beam method over Pd(110) and Pd(111). The CO2 formation rate is temperature dependent under various partial pressure conditions. The temperature of the maximum formation rate is denoted as TSmax. Analyses of IR emission spectra at surface temperatures higher than TSmax showed that the average vibrational temperature (TVAV) is higher for Pd(111) than for Pd(110). The antisymmetric vibrational temperature (TVAS) is almost equal on both surfaces. These results suggest that the activated CO2 complex is more bent on Pd(111) and straighter on Pd(110). Furthermore, the difference in the TVAV value was small for surface temperatures less than TSmax. The TVAS value was much higher than TVAV on both surfaces. These phenomena were observed only when the surface temperature was lower than TSmax: they became more pronounced at lower temperatures, suggesting that the activated complex of CO2 formation is much straighter on both Pd surfaces than that observed at higher surface temperatures. Combined with kinetic results, the higher CO coverage at the lower surface temperatures is inferred to be related to the linear activated complex of CO2 formation.     

Isotopic exchange of CO adsorbed on Pt(111)

The isotopic exchange of CO adsorbed on Pt(111) was studied using polarization modulation IR reflection absorption spectroscopy (PM-IRRAS) and temperature programmed desorption. It was found that the rate constants for the exchange reaction are much higher than would be expected from previous investigations of CO adsorbed on Pt nanoparticles. The adsorption of CO on Pt(111) under elevated pressures of CO and H(2) was also studied using PM-IRRAS. It was seen that CO pressures above 1 mbar lead to a shift in the absorption peak arising from CO adsorbed on a bridge site from 1850 to 1875 cm(-1). Exposing the CO-covered Pt(111) surface to 1000 mbar H(2) did not lead to any significant desorption of CO at room temperature, whereas at 363 K H(2) exposure did lead to a significant desorption of CO, due to the increased chemical potential of H(2). In a mixture of CO and H(2) with partial pressures of 0.01 mbar and 1000 mbar, respectively, no significant effect of H(2) on the PM-IRRAS spectrum was seen at temperatures below 423 K.     

M(mu-CN)Fe(mu-CN)M' chains with phthalocyanine iron centers: preparation, structures, and isomerization

The molecular building blocks Fe(II)Pc (Pc = phthalocyaninato2-), Fe(III)Pc, ZnPc, Cp(dppe)Fe, and Cp(PPh3)2Ru were combined in the cyanide-bridged dinuclear reference compounds with M-CN-ZnPc and M-CN-FePc-CN arrays containing Fe(II)Pc and Fe(III)Pc. The linear trinuclear species with the M(mu-CN)Fe(mu-CN)M' backbone were prepared for both Fe(II)Pc and Fe(III)Pc centers, for terminal Fe/Fe, Fe/Ru, and Ru/Ru combinations and for all three possible cyanide orientations (M-CN-Fe-NC-M', M-CN-Fe-CN-M', and M-NC-Fe-CN-M'). The 15 complexes obtained were identified from their IR spectra and six structure determinations. The preferred orientation of the cyanide bridges could be established starting from the [Fe-NC-Fe(III)Pc-CN-Fe]+ complex, which is labile in solution and isomerizes to the corresponding [Fe-CN-Fe(III)Pc-NC-Fe]+ complex. A kinetic analysis of this isomerization has yielded an activation barrier of roughly 110 kJ/mol.     

The C3-bending levels of the C3-Ar complex studied by optical spectroscopy and ab initio calculation

The A-X electronic transition of C3-Ar, near 405 nm, has been studied by both laser-induced fluorescence and wavelength-resolved emission techniques. Emission spectra have been recorded from 14 vibrational levels of the A state of C3-Ar; these spectra consist of progressions in the ground state v2 and v4 vibrations (the in- and out-of-plane C3-bending motions, respectively). With increasing bending excitation, these ground state levels shift progressively downwards compared to those of free C3, indicating that the van der Waals complexes are becoming more tightly bound. The level structure of the two vibrations of C3-Ar has been fitted to a perturbed harmonic oscillator model, where the potential function has the form V = V1r cos theta + V2r2 cos 2theta (r is the amplitude of the C3-bending motion and theta gives the orientation of the rare gas atom relative to the plane of the bent C3 molecule). Ab initio calculations have been carried out for C3-Ar at the coupled-cluster singles, doubles (and triples)/correlation consistent polarization valence quadruple-zeta level. They predict that the C3-Ar complex is nearly T shaped at equilibrium, and that as the C3 molecule bends away from the linear configuration, the preferred orientation is "arrow" shaped. From the results of the best fit to the model and the emission spectral intensities, the relative orientation of the out-of-plane pi electron of the A-state complex and the Ar atom has been estimated. No bands of the Ar complex were found near the C3, A-X, (0,0) band, consistent with the fact that the A 1Piu, upsilon = 0 level of free C3 is strongly perturbed by triplet levels. In the excitation spectra of the Ar complex, the bands with upsilonb' > 0 show redshifts of about 16-36 cm(-1) compared to those of free C3, indicating that the A-state complex in these levels is more tightly bonded than the X-state complex.     

(110)晶面全择优取向Cu镀层的制备及其条件优化

研究了添加剂聚乙二醇(PEG)、氯离子(Cl－)和电流密度对Cu的电沉积过程的影响, 着重探讨了制备(110)晶面全择优取向Cu镀层的电沉积条件及其形成机理. 循环伏安(CV)结果表明, PEG阻化Cu的电沉积, Cl－加快Cu的电沉积速率. XRD实验结果表明, PEG和Cl－在一定浓度范围有利于(110)晶面择优取向; 这两种不同特性的添加剂的协同作用可以制得(110)晶面全择优取向的较薄的Cu镀层; 所制备的全择优Cu镀层较稳定. 全择优取向Cu镀层形成的机理在于PEG和Cl－吸附过程联合起作用, 在不同晶粒的不同晶面进行选择吸附, 改变了晶面的生长速率及晶粒的快生长方向.