Mechanism of titanium-nitride chemical mechanical polishing

During the preparation of the phase change memory,the deposition and chemical mechanical polishing(CMP)of titanium nitride(TiN)are indispensable.A new acidic slurry added with sodium hypochlorite(NaClO)as an oxidizer is developed for the CMP of TiN film.It has achieved a material removal rate of 76 nm/min,a high selectivity between TiN film and silica(SiO_(2))films of 128:1,a selectivity between TiN film and tungsten film of 84:1 and a high surface quality.To understand the mechanism of TiN CMP process,x-ray photoelectron(XPS)spectroscope and potentiodynamic polarization measurement are performed.It is found that the mechanism of TiN CMP process is cyclic reaction polishing mechanism.In addition,both static corrosion rate and the inductively coupled plasma results indicate TiN would not be dissolved,which means that the mechanical removal process of oxide layer plays a decisive role in the material removal rate.Finally,the mechanism of TiN polishing process is given based on the analysis of surface potential and the description of blocking function.

Chemical Mechanical Polishing of Glass Substrate with α-Alumina-g-Polystyrene Sulfonic Acid Composite Abrasive

Abrasive is the one of key influencing factors during chemical mechanical polishing（CMP） process. Currently, α-Alumina （α-Al2O3） particle, as a kind of abrasive, has been widely used in CMP slurries, but their high hardness and poor dispersion stability often lead to more surface defects. After being polished with composite particles, the surface defects of work pieces decrease obviously. So the composite particles as abrasives in slurry have been paid more attention. In order to reduce defect caused by pure α-Al2O3 abrasive, α-alumina-g-polystyrene sulfonic acid （α-Al2O3-g-PSS） composite abrasive was prepared by surface graft polymerization. The composition, structure and morphology of the product were characterized by Fourier transform infrared spectroscopy（FTIR）, X-ray photoelectron spectroscopy（XPS）, time-of-flight secondary ion mass spectroscopy（TOF-SIMS）, and scanning electron microscopy（SEM）, respectively. The results show that polystyrene sulfonic acid grafts onto α-Al2O3, and has well dispersibility. Then, the chemical mechanical polishing performances of the composite abrasive on glass substrate were investigated with a SPEEDFAM-16B-4M CMP machine. Atomic force microscopy（AFM） images indicate that the average roughness of the polished glass substrate surface can be decreased from 0.835 nm for pure α-Al2O3 abrasive to 0.583 nm for prepared α-Al2O3-g-PSS core-shell abrasive. The research provides a new and effect way to improve the surface qualities during CMP.

Research on Abrasives in the Chemical Mechanical Polishing Process for Silicon Nitride Balls

Silicon nitride (Si 3N 4) has been the main material for balls in ceramic ball bearings, for its lower density, high strength, high hardness, fine thermal stability and anticorrosive, and is widely used in various fields, such as high speed and high temperature areojet engines, precision machine tools and chemical engineer machines. Silicon nitride ceramics is a kind of brittle and hard material that is difficult to machining. In the traditional finishing process of silicon nitride balls, balls are lapped by expensive diamond abrasive. The machining is inefficiency and the cost is high, but also lots of pits, scratch subsurface micro crazes and dislocations will be caused on the surface of the balls, the performance of the ball bearings would be declined seriously. In these year, a kind of new technology known as chemical mechanical polishing is introduced in the ultraprecision machining process of ceramic balls. In this technology, abrasives such as ZrO 2, CeO 2 whose hardness is close to or lower than the work material (Si 3N 4) are used to polishing the balls. In special slurry, these abrasives can chemo-mechanically react with the work material and environment (air or water) to generate softer material (SiO 2). And the resultants will be removed easily at 0.1 nm level. So the surface defects can be minimized, very smooth surface (Ra=4 nm) and fine sphericity (0.15～0.25 μm ) can be obtained, and the machining efficiency is also improved. The action mechanism of the abrasives in the chemical mechanical polishing process in finishing of silicon nitride ball will be introduced in this paper.

Preparation of Non-spherical Colloidal Silica Nanoparticle and Its Application on Chemical Mechanical Polishing of Sapphire

Non-spherical colloidal silica nanoparticle was prepared by a simple new method, and its particle size distribution and shape morphology were characterized by dynamic light scattering(DLS) and the Focus Ion Beam(FIB) system. This kind of novel colloidal silica particles can be well used in chemical mechanical polishing(CMP) of sapphire wafer surface. And the polishing test proves that non-spherical colloidal silica slurry shows much higher material removal rate(MRR) with higher coefficient of friction(COF) when compared to traditional large spherical colloidal silica slurry with particle size 80 nm by DLS. Besides, sapphire wafer polished by non-spherical abrasive also has a good surface roughness of 0.460 6 nm. Therefore, non-spherical colloidal silica has shown great potential in the CMP field because of its higher MRR and better surface roughness.

A nano-scale mirror-like surface of Ti–6Al–4V attained by chemical mechanical polishing

Metal Ti and its alloys have been widely utilized in the fields of aviation, medical science, and micro-electromechanical systems, for its excellent specific strength, resistance to corrosion, and biological compatibility. As the application of Ti moves to the micro or nano scale, however, traditional methods of planarization have shown their short slabs.Thus, we introduce the method of chemical mechanical polishing（CMP） to provide a new way for the nano-scale planarization method of Ti alloys. We obtain a mirror-like surface, whose flatness is of nano-scale, via the CMP method. We test the basic mechanical behavior of Ti–6Al–4V（Ti64） in the CMP process, and optimize the composition of CMP slurry.Furthermore, the possible reactions that may take place in the CMP process have been studied by electrochemical methods combined with x-ray photoelectron spectroscopy（XPS）. An equivalent circuit has been built to interpret the dynamic of oxidation. Finally, a model has been established to explain the synergy of chemical and mechanical effects in the CMP of Ti–6Al–4V.

Effect of Abrasive Concentration on Chemical Mechanical Polishing of Sapphire

Effects of abrasive concentration on material removal rate CMRR） and surtace quality m the chemical mecnamcal polishing （CMP） of light-emitting diode sapphire substrates are investigated. Experimental results show that the MRR increases linearly with the abrasive concentration, while the rms roughness decreases with the increasing abrasive concentration. In addition, the in situ coefficient of friction （COF） is also conducted during the sapphire polishing process. The results present that COF increases sharply with the abrasive concentration up to 20 wt% and then shows a slight decrease from 20wt% to 40wt%. Temperature is a product of the friction force that is proportional to COF, which is an indicator for the mechanism of the sapphire CMP.

TWO STEPS CHEMICAL-MECHANICAL POLISHING OF RIGID DISK SUBSTRATE TO GET ATOM-SCALE PLANARIZATION SURFACE

In order to get atomic smooth rigid disk substrate surface, ultra-fined alumina slurry and nanometer silica slurry are prepared, and two steps chemical-mechanical polishing （CMP） of rigid disk substrate in the two slurries are studied. The results show that, during the first step CMP in the alumina slurry, a high material removal rate is reached, and the average roughness （Ra） and the average waviness （Wa） of the polished surfaces can be decreased from previous 1.4 nm and 1.6 nm to about 0.6 nm and 0.7 nm, respectively. By using the nanometer silica slurry and optimized polishing process parameters in the second step CMP, the Ra and the Wa of the polished surfaces can be further reduced to 0.038 nm and 0.06 am, respectively. Atom force microscopy （AFM） analysis shows that the final polished surfaces are ultra-smooth without micro-defects.

Theoretical and experimental investigation of chemical mechanical polishing of W–Ni–Fe alloy

Fine finishing of tungsten alloy is required to improve the surface quality of molds and precision instruments. Nevertheless, it is difficult to obtain high-quality surfaces as a result of grain boundary steps attributed to differences in properties of two-phase microstructures. This paper presents a theoretical and experimental investigation on chemical mechanical polishing of W–Ni–Fe alloy. The mechanism of the boundary step generation is illustrated and a model of grain boundary step formation is proposed. The mechanism reveals the effects of mechanical and chemical actions in both surface roughness and material removal. The model was verified by the experiments and the results show that appropriately balancing the mechanical and chemical effects restrains the generation of boundary steps and leads to a fine surface quality with a high removal rate by citric acid-based slurry.

Study of Chemical Etching and Chemo-Mechanical Polishing on CdZnTe Nuclear Detectors

Cadmium zinc telluride (CdZnTe) semiconductor has applications in the detection of X-rays and gamma-rays at room temperature without having to use a cooling system. Chemical etching and chemo-mechanical polishing are processes used to smoothen CdZnTe wafer during detector device fabrication. These processes reduce surface damages left after polishing the wafers. In this paper, we compare the effects of etching and chemo-mechanical polishing on CdZnTe nuclear detectors, using a solution of hydrogen bromide in hydrogen peroxide and ethylene glycol mixture. X-ray photoelectron spectroscopy (XPS) was used to monitor TeO2 on the wafer surfaces. Current-voltage and detector-response measurements were made to study the electrical properties and energy resolution. XPS results showed that the chemical etching process resulted in the formation of more TeO2 on the detector surfaces compared to chemo-mechanical polishing. The electrical resistivity of the detector is of the order of 1010 Ω-cm. The chemo-mechanical polishing process increased the leakage current more that chemical etching. For freshly treated surfaces, the etching process is more detrimental to the energy resolution compared to chemo-mechanically polishing.

Iron trichloride as oxidizer in acid slurry for chemical mechanical polishing of Ge_2Sb_2Te_5

The effect of iron trichloride （FeC13） on chemical mechanical polishing （CMP） of Ge2Sb2Te5 （GST） film is inves- tigated in this paper. The polishing rate of GST increases from 38 nm/min to 144 nm/min when the FeC13 concentration changes from 0.01 wt% to 0.15 wt%, which is much faster than 20 nm/min for the 1 wt% H2O2-based slurry. This polish- ing rate trends are inversely correlated with the contact angle data of FeCl3-based slurry on the GST film surface. Thus, it is hypothesized that the hydrophilicity of the GST film surface is associated with the polishing rate during CMP. Atomic force microscope （AFM） and optical microscope （OM） are used to characterize the surface quality after CMP. The chemical mechanism is studied by potentiodynamic measurements such as Ecorr and Icorr to analyze chemical reaction between FeCl3 and GST surface. Finally, it is verified that slurry with FeCl3 has no influence on the electrical property of the post-CMP GST film by the resistivity-temperature （RT） tests.

Electrochemical characteristic of chemical-mechanical polishing of copper with oxide passive film

Electrochemical behavior of chemical mechanical polishing of copper with oxide passive film was studied by electrochemical measurement technologies. Dependences of polarization curves and electrochemical parameters, the rate of formation or removal of passive film of copper on film modifier KClO 3 were investigated. The rules of dependences of corrosion potentials and corrosion current densities on polishing pressure and rotation rate were obtained. It is discovered that the rates of formation and removal of passive film of copper are enhanced, while the polishing pressure and rotation rate are reduced. The experiments show that the CMP processes decrease Tafel slope, increase electron transfer coefficient of anode reaction and decrease the activation energy of corrosion reaction of copper, thereby the corrosion processes are accelerated. The results indicate that CMP slurry recipe, which is composed of NaAc NaOH medium, using KClO 3 as passive film modifier and nano sized γ Al 2O 3 as abrasive, is feasible and reasonable. The technological conditions are 100 r/min, 16 kPa.

8寸CMP设备对小尺寸镀铜InP晶圆的工艺开发

为了实现在8寸化学机械抛光设备上进行小尺寸镀铜InP晶圆的减薄抛光工作,提高设备的兼容性,缩减工艺步骤,减少过多操作导致InP晶圆出现裂纹暗伤和表面颗粒增加等问题,自制特殊模具,使小尺寸InP晶圆在8寸化学机械抛光设备上进行加工,再根据InP晶圆易碎的缺陷问题,通过调整设备的抛光头压力、转速和抛光垫的转速等相关工艺参数,使其满足后续键合工艺的相关需求。实验结果表明:在使用特殊模具下,当抛光头的压力调整为20.684 kPa、抛光头与抛光垫的转速分别为:93 r/min和87 r/min时,InP晶圆的表面粗糙度达到:Ra≤1 nm;表面铜层的去除速率达到3857×10^(-10)/min;后续与8寸晶圆的键合避免键合位置出现空洞等缺陷,实现2寸InP晶圆在8寸设备上的CMP工艺,大大降低了CMP工艺成本,同时避免晶圆在转移过程中出现表面颗粒度增加和划伤的情况,实现了InP晶圆与Si晶圆的异质键合及Cu互连工艺。

Two material removal modes in chemical mechanical polishing:mechanical plowing vs.chemical bonding

With the rapid development of semiconductors,the number of materials needed to be polished sharply increases.The material properties vary significantly,posing challenges to chemical mechanical polishing(CMP).Accordingly,the study aimed to classify the material removal mechanism.Based on the CMP and atomic force microscopy results,the six representative metals can be preliminarily classified into two groups,presumably due to different material removal modes.From the tribology perspective,the first group of Cu,Co,and Ni may mainly rely on the mechanical plowing effect.After adding H_(2)O_(2),corrosion can be first enhanced and then suppressed,affecting the surface mechanical strength.Consequently,the material removal rate(MRR)and the surface roughness increase and decrease.By comparison,the second group of Ta,Ru,and Ti may primarily depend on the chemical bonding effect.Adding H_(2)O_(2)can promote oxidation,increasing interfacial chemical bonds.Therefore,the MRR increases,and the surface roughness decreases and levels off.In addition,CMP can be regulated by tuning the synergistic effect of oxidation,complexation,and dissolution for mechanical plowing,while tuning the synergistic effect of oxidation and ionic strength for chemical bonding.The findings provide mechanistic insight into the material removal mechanism in CMP.

Atomistic understanding of rough surface on the interfacial friction behavior during the chemical mechanical polishing process of diamond

The roughness of the contact surface exerts a vital role in rubbing.It is still a significant challenge to understand the microscopic contact of the rough surface at the atomic level.Herein,the rough surface with a special root mean square(RMS)value is constructed by multivariate Weierstrass–Mandelbrot(W–M)function and the rubbing process during that the chemical mechanical polishing(CMP)process of diamond is mimicked utilizing the reactive force field molecular dynamics(ReaxFF MD)simulation.It is found that the contact area A/A0 is positively related with the load,and the friction force F depends on the number of interfacial bridge bonds.Increasing the surface roughness will increase the friction force and friction coefficient.The model with low roughness and high lubrication has less friction force,and the presence of polishing liquid molecules can decrease the friction force and friction coefficient.The RMS value and the degree of damage show a functional relationship with the applied load and lubrication,i.e.,the RMS value decreases more under larger load and higher lubrication,and the diamond substrate occurs severer damage under larger load and lower lubrication.This work will generate fresh insight into the understanding of the microscopic contact of the rough surface at the atomic level.

阴/非离子型表面活性剂对CMP后SiO_(2)颗粒的去除效果

为了更有效地去除铜晶圆化学机械抛光(CMP)后清洗残留的SiO_(2)颗粒,选择了2种阴离子型表面活性剂(SLS、TD⁃40)和2种非离子型表面活性剂(AEO⁃5、JFC⁃6),通过接触角、表面张力、电化学、分子动力学模拟实验探究了4种表面活性剂在铜表面的润湿性、吸附构型及吸附稳定性。通过优化表面活性剂质量浓度,选择达到吸附稳定时的质量浓度配置4种表面活性剂来清洗铜晶圆,利用扫描电子显微镜观测铜表面形貌,对比它们的清洗效果。随后选择TD⁃40和JFC⁃6进行复配,研究复配后表面活性剂对硅溶胶颗粒的去除效果。实验结果表明,使用体积比为2∶1的TD⁃40与JFC⁃6进行复配得到的CMP清洗液对SiO_(2)颗粒的去除效果比单一表面活性剂的更好。

磨粒振动对碳化硅CMP的微观结构演变和材料去除的影响

针对化学机械抛光中磨料易团聚、机械和化学作用不能充分发挥等问题,采用振动辅助的方法进行优化。通过分子动力学模拟,分析磨粒振动的频率、振幅及其压入深度、划切速度对工件表面微观原子迁移的演变规律,揭示振动对材料去除和表面改善的促进机制;并通过振动辅助化学机械抛光工艺试验和表面成分分析,验证振动辅助的抛光效果和去除机制。结果表明:适当增大磨粒的振动频率、振动振幅及其压入深度、划切速度,可有效提高工件表面的原子势能和温度;磨粒振动有利于提高工件表面原子的混乱度,促进碳化硅参与氧化反应,形成氧化层并以机械方式去除;抛光试验和成分分析也证实振动可以提高材料去除率约50.5%,改善表面质量约25.4%。

蓝宝石衬底CMP中氧化硅磨粒粒度分布对抛光液体系性能影响研究

目的 化学机械抛光(CMP)包含化学腐蚀和机械磨削两方面,抛光液p H、磨粒粒径和浓度等因素均会不同程度地影响其化学腐蚀和机械磨削能力,从而影响抛光效果。方法 采用30~150 nm连续粒径磨粒抛光液、120 nm均一粒径磨粒抛光液、50 nm和120 nm配制而成的混合粒径磨粒抛光液,分别对蓝宝石衬底晶圆进行循环CMP实验,研究CMP过程中抛光液体系的变化。结果 连续粒径磨粒抛光液中磨粒大规模团聚,满足高材料去除率的抛光时间仅有4 h,抛光后的晶圆表面粗糙度为0.665 nm;均一粒径磨粒抛光液中磨粒稳定,无团聚现象,抛光9 h内材料去除率较连续粒径磨粒抛光液高94.7%,能至少维持高材料去除率18 h,抛光后的晶圆表面粗糙度为0.204 nm;混合粒径磨粒抛光液初始状态下磨粒稳定性较高,抛光9 h内材料去除率较连续粒径磨粒抛光液高114.8%,之后磨粒出现小规模团聚现象,后9h材料去除率仅为均一粒径磨粒抛光液的59.6%,18 h内材料去除率仅为均一粒径磨粒抛光液的87.7%,但抛光后的晶圆表面粗糙度为0.151 nm。结论 一定时间内追求较高的材料去除率和较好的晶圆表面粗糙度选用混合粒径磨粒抛光液,但需要长时间CMP使用均一粒径磨粒抛光液更适合,因此,在工业生产中需要根据生产要求配合使用混合粒径磨粒抛光液和均一粒径磨粒抛光液。

半导体材料CMP过程中磨料的研究进展

对磨料在半导体材料化学机械抛光(CMP)中的应用和研究进展进行了简单阐述,从各代半导体材料制成半导体器件的加工要求介绍了磨料在半导体材料CMP中的重要性,从CMP过程中磨料与半导体材料的相互作用介绍了磨料在半导体材料CMP中的环保性,从磨料的改性和制备介绍了磨料在半导体材料CMP中应用的限制性,重点从半导体材料的去除速率和表面质量介绍了磨料对半导体材料抛光性能的影响,并对国内外研究中单一磨料、混合磨料和复合磨料对半导体材料抛光性能的影响进行了评述,总结了近年来磨料在半导体材料CMP中的研究进展。最后,对磨料在半导体材料CMP中存在的共性问题进行了总结,并对该领域所面临的挑战及发展方向进行了展望。

Electrochemical behavior and polishing properties of silicon wafer in alkaline slurry with abrasive CeO_2

The electrochemical behavior of silicon wafer in alkaline slurry with nano-sized CeO2 abrasive was investigated.The variations of corrosion potential(φcorr)and corrosion current density(Jcorr)of the P-type(100)silicon wafer with the slurry pH value and the concentration of abrasive CeO2 were studied by polarization curve technologies.The dependence of the polishing rate on the pH and the concentration of CeO2 in slurries during chemical mechanical polishing(CMP)were also studied.It is discovered that there is a large change of φcorr and Jcorr when slurry pH is altered and the Jcorr reaches the maximum(1.306 μA/cm2)at pH 10.5 when the material removal rate(MRR)comes to the fastest value.The Jcorr increases gradually from 0.994 μA/cm2 with 1% CeO2 to 1.304 μA/cm2 with 3% CeO2 and reaches a plateau with the further increase of CeO2 concentration.There is a considerable MRR in the slurry with 3% CeO2 at pH 10.5.The coherence between Jcorr and MRR elucidates that the research on the electrochemical behavior of silicon wafers in the alkaline slurry could offer theoretic guidance on silicon polishing rate and ensure to adjust optimal components of slurry.