Polydisperse spherical colloidal silica particles:Preparation and application

A new industrial method has been developed to produce polydisperse spherical colloidal silica particles with a very broad particle size,ranging from 20-95 nm.The process uses a reactor in which the original seed solution is heated to 100 ℃,and then active silicic acid and the seed solution are titrated to the reactor continuously with a constant rate.The original seeds and the titrated seeds in the reactor will go through different particle growth cycles to form different particle sizes.Both the particles' size distribution and morphology have been characterized by dynamic light scattering(DLS)and the focus ion beam(FIB) system.In addition,the as-prepared polydisperse colloidal silica particle in the application of sapphire wafer's chemical mechanical polishing(CMP) process has been tested.The material removal rate(MRR) of this kind of abrasive has been tested and verified to be much faster than traditional monodisperse silica particles.Finally,the mechanism of sapphire CMP process by this kind of polydisperse silica particles has been investigated to explore the reasons for the high polishing rate.     

Study on sapphire removal for thin-film LEDs fabrication using CMP and dry etching

Mechanical grinding, chemical mechanical polishing (CMP) and dry etching process are integrated to remove sapphire substrate for fabricating thin-film light-emitting diodes. The thinning of sapphire substrate is done by fast mechanical grinding followed by CMP. The CMP can remove or reduce most of the scratches produced by mechanical grinding, recovering both the mechanical strength and wafer warpage to their original status and resulting in a smoother surface. The surface morphology and surface roughness on grinded and polished sapphire substrate are measured by using atomic force microscopy (AFM). The etch rates of sapphire by BCl₃-based dry etching are reported. Pattern transfer to the physical and chemical stability of sapphire is made possible by inductively coupled plasma (ICP) etch system that generates high density plasma. The patterning of several microns period in sapphire wafer by using a combination of BCl₃/Ar plasma chemistry and SiO₂ mask is presented. The anisotropic etch profile formed on sapphire wafer is obtained from scanning electron microscopy (SEM) images.     

Preparation of monodisperse polystyrene/silica core-shell nano-composite abrasive with controllable size and its chemical mechanical polishing performance on copper

Monodisperse silica-coated polystyrene (PS) nano-composite abrasives with controllable size were prepared via a two-step process. Monodisperse positively charged PS colloids were synthesized via polymerization of styrene by using a cationic initiator. In the subsequent coating process, silica formed shell on the surfaces of core PS particles via the ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane. Neither centrifugation/water wash/redispersion cycle process nor surface modification or addition surfactant was needed in the whole process. The morphology of the abrasives was characterized by scanning electron microscope. Transmission electron microscope and energy dispersive X-ray analysis results indicated that silica layer was successfully coated onto the surfaces of PS particles. Composite abrasive has a core-shell structure and smooth surface. The chemical mechanical polishing performances of the composite abrasive and conventional colloidal silica abrasive on blanket copper wafers were investigated. The root mean square roughness decreases from 4.27 nm to 0.56 nm using composite abrasive. The PS/SiO₂ core-shell composite abrasives exhibited little higher material removal rate than silica abrasives.     

Effects of the ultrasonic flexural vibration on the interaction between the abrasive particles; pad and sapphire substrate during chemical mechanical polishing (CMP)

In this paper, the technique of ultrasonic flexural vibration assisted chemical mechanical polishing (UFV-CMP) was used for sapphire substrate CMP. The functions of the polishing pad, the silica abrasive particles, and the chemical additives of the slurry such as pH value regulator and dispersant during the sapphire's UFV-CMP were investigated. The results showed that the actions of the ultrasonic and silica abrasive particles were the main factors in the sapphire material removal rate (MMR) and the chemical additives were helpful to decrease the roughness of sapphire. Then the effects of the flexural vibration on the interaction between the silica abrasive particles, pad and sapphire substrate from the kinematics and dynamics were investigated to explain why the MRR of UFV-CMP was bigger than that of the traditional CMP. It indicated that such functions improved the sapphire's MRR: the increasing of the contact silica particles’ motion path lengths on the sapphire's surface, the enhancement of the contact force between the contact silica particles and the sapphire's surface, and the impaction of the suspending silica particles to the sapphire's surface.     

Preparation of alumina/silica core-shell abrasives and their CMP behavior

Abrasive is one of key influencing factors on the surface quality during the chemical mechanic polishing (CMP). α-Alumina particles, as a kind of widely used abrasive in CMP slurries, often cause to surface defects because of its high hardness. In the present paper, a series of novel alumina/silica core-shell abrasives in slurries were described. The CMP performances of the alumina/silica core-shell abrasives on hard disk substrate were investigated by using a SPEEDFAM-16B-4M CMP equipment. Experimental results indicate that the CMP performances are strong dependent on the coated SiO₂ content of the alumina/silica composite abrasives. Slurries containing the alumina/silica composite abrasives exhibited lower surface roughness and waviness as well as lower topographical variations and less scratch than that containing pure alumina abrasive under the same testing conditions.     

Removal of scratch on the surface of MgO single crystal substrate in chemical mechanical polishing process

Etching and chemical mechanical polishing (CMP) experiments of the MgO single crystal substrate with an artificial scratch on its surface are respectively performed with the developed polishing slurry mainly containing 2 vol.% phosphoric acid (H₃PO₄) and 10-20 nm colloidal silica particles, through observing the variations of the scratch topography on the substrate surface in experiments process, the mechanism and effect of removing scratch during etching and polishing are studied, some evaluating indexes for effect of removing scratch are presented. Finally, chemical mechanical polishing experiments of the MgO substrates after lapped are conducted by using different kinds of polishing pads, and influences of the polishing pad hardness on removal of the scratches on the MgO substrate surface are discussed.     

Ultrasonic flexural vibration assisted chemical mechanical polishing for sapphire substrate

The sapphire substrates are polished by traditional chemical mechanical polishing (CMP) and ultrasonic flexural vibration (UFV) assisted CMP (UFV-CMP) respectively with different pressures. UFV-CMP combines the functions of traditional CMP and ultrasonic machining (USM) and has special characteristics, which is that ultrasonic vibrations of the rotating polishing head are in both horizontal and vertical directions. The material removal rates (MRRs) and the polished surface morphology of CMP and UFV-CMP are compared. The MRR of UFV-CMP is two times larger than that of traditional CMP. The surface roughness (root mean square, RMS) of the polished sapphire substrate of UFV-CMP is 0.83 Å measured by the atomic force microscopy (AFM), which is much better than 2.12 Å obtained using the traditional CMP. And the surface flatness of UFV-CMP is 0.12 μm, which is also better than 0.23 μm of the traditional CMP. The results show that UFV-CMP is able to improve the MRR and finished surface quality of the sapphire substrates greatly. The material removal and surface polishing mechanisms of sapphire in UFV-CMP are discussed too.     

Process characterization and statistical analysis of oxide CMP on a silicon wafer with sparse data

Continuous advancements in chemical mechanical planarization (CMP) process, such as new polishing pads, slurry materials, and abrasive particles necessitate optimization of the key process input parameters for maximum material removal rate (MRR) and/or minimum within wafer non-uniformity (WIWNU) using sparse experimental results. In this investigation a methodology is proposed for developing process models and optimization of input parameters (both main and interaction parameters) for maximum MRR and minimum WIWNU. This approach will be equally applicable for polishing other materials, such as copper, dielectrics and low-k materials. Complex relationships exist between several machine-specific and material-specific input parameters and the output performance variables, chiefly MRR and WIWNU. However, only a few of the input parameters are changed on a regular basis. Hence, only those subsets of relationships need to be considered for optimizing the CMP process. In this investigation, CMP process was characterized for polishing a thin layer of silicon dioxide on top of a silicon wafer. Statistical analysis of the experimental data was performed to obtain the order of significance of the input variables (machine and material parameters and their interactions). Both linear and logarithmic regression models were developed and used to determine optimum process conditions for maximizing MRR and minimizing WIWNU. While the main input parameters were responsible for maximum MRR, interaction parameters were found to be responsible for minimizing WIWNU. This may vary for different materials and polishing environments. PACS 81.00.00; 81.05.Gc; 81.65.Ps     

The effect of chemical polishing on the interface structure and electrical property of Au/Cd0.9Zn0.1Te contact

The interface structures between Au electrode and Cd_0.9Zn_0.1Te wafer with different surface treatments are studied by means of transmission electron microscopy. Before the preparation of the Au film, atomic force microscopy and scanning electron microscopy are employed to investigate the surface morphology and elemental concentration before and after the chemical polishing process. It is found that an amorphous layer with the thickness of approximately 5 nm exists at the interface area for the only mechanical polished samples. As the chemical polishing process goes on, the interfaces become flatter and smoother. A thinner lattice mismatch layer instead of the amorphous layer after the chemical polishing process is found between Au and Cd_0.9Zn_0.1Te. The formation mechanism for the amorphous layer is considered to be the large lattice mismatch between Au and matrix. Furthermore, current–voltage (I–V) measurement is also carried out to investigate the relationship between the interface structure and electrical properties. The ohmic contact coefficient is calculated to increase from 0.4609 to 1.0904 after 4 min chemical polishing corresponding to the I–V test. It is indicated that the charges become easier to move across the interface, which has no amorphous layer, due to the weaker blocking effect to the charges for the thinner and ordered interface region.     

Effect of additives for higher removal rate in lithium niobate chemical mechanical planarization

High roughness and a greater number of defects were created by lithium niobate (LN; LiNbO₃) processes such as traditional grinding and mechanical polishing (MP), should be decreased for manufacturing LN device. Therefore, an alternative process for gaining defect-free and smooth surface is needed. Chemical mechanical planarization (CMP) is suitable method in the LN process because it uses a combination approach consisting of chemical and mechanical effects. First of all, we investigated the LN CMP process using commercial slurry by changing various process conditions such as down pressure and relative velocity. However, the LN CMP process time using commercial slurry was long to gain a smooth surface because of lower material removal rate (MRR). So, to improve the material removal rate (MRR), the effects of additives such as oxidizer (hydrogen peroxide; H₂O₂) and complexing agent (citric acid; C₆H₈O₇) in a potassium hydroxide (KOH) based slurry, were investigated. The manufactured slurry consisting of H₂O₂-citric acid in the KOH based slurry shows that the MRR of the H₂O₂ at 2 wt% and the citric acid at 0.06 M was higher than the MRR for other conditions.     

Nanopolishing of silicon wafers using ultrafine-dispersed diamonds

In the present study, two new methods are proposed for the polishing of silicon wafers using ultrafine-dispersed diamonds (UDDs). The first proposed polishing method uses a polishing tool with an ultrafine abrasive material made through the electrophoretic deposition of UDDs onto a brass rod. Dry polishing tests showed that the surface roughness of the silicon wafer was reduced from R_a=107 to 4 nm after polishing for 30 min. The second method uses a new polishing pad with self-generating porosity. By polishing with the new pad in combination with the polycrystalline UDD in a water suspension, it is possible to achieve the specified surface roughness of the silicon wafer much faster than when using a conventional pad made of foamed polyurethane. The tests showed that the surface roughness of the silicon wafer was reduced from R_a=107 to 2 nm after polishing for 90 min.     

Polishing behavior of PS/CeO2 hybrid microspheres with controlled shell thickness on silicon dioxide CMP

Organic-inorganic composite microspheres with PS as a core and CeO₂ nanoparticles as a shell were synthesized by in situ decomposition reaction of Ce(NO₃)₃ on the surfaces of PS microspheres prepared through soap-free emulsion polymerization. The shell thickness of the composite microspheres could be turned by varying the concentration of Ce(NO₃)₃ in the reaction solution. The whole process required neither surface treatment for PS microspheres nor additional surfactant or stabilizer. The as-synthesized PS/CeO₂ composite microsphere samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Oxide chemical mechanical polishing (CMP) performance of the PS/CeO₂ composite abrasives with different shell thickness was characterized by atomic force microscopy (AFM). The results indicated that the as-prepared core-shell structured composite microspheres (220-260 nm in diameter) possessed thin shell (10-30 nm) composed of CeO₂ nanoparticles (particle diameter of 5-10 nm), and the final CeO₂ contents of the composite microspheres ranged from 10 to 50 wt%. A possible mechanism for the formation of PS/CeO₂ composite microspheres was discussed also. The CMP test results confirmed that the novel core-shell structured composite abrasives are useful to improve oxide CMP performance. In addition, there is an obvious effect of shell thickness of the composite abrasives on oxide CMP performance.     

无损伤超光滑LBO晶体表面抛光方法研究

传统的抛光LBO晶体的方法是选用金刚石抛光粉在沥青抛光盘上抛光。沥青盘易于变形不容易修整,金刚石粉特别硬容易损伤抛光晶体表面。抛光过程中,抛光盘和抛光粉的选择是非常重要的,直接影响到抛光效率和最终的表面质量。新的抛光LBO晶体的方法,其抛光过程是一个化学机械过程,抛光盘、抛光粉和抛光材料相互作用。选用两种抛光盘(培纶和聚氨酯盘),三种较软的抛光磨料(CeO2,Al2O3和SiO2胶体),并在LBO晶体的(001)面进行抛光实验。用原子力显微镜测量和分析了表面粗糙度。结果表明,使用聚氨酯盘和SiO2胶体能够获得无损伤超光滑的LBO晶体表面,其表面粗糙度的RMS为0.3nm。     

Mechanism of the interaction between Al2O3 and SiO2 during the chemical-mechanical polishing of sapphire with silicon dioxide

Chemical-mechanical polishing of sapphire with colloidal silicon dioxide has been studied with X-ray photoelectron spectroscopy. It has been found that aluminum silicate with the composition Al₂SiO₅ is formed on the polished crystal surface. The silicon-containing layer thickness reaches 20.5 nm. Its value decreases in the sequence of samples with (0001), ((10[`1]\bar 12), and (11[`2]\bar 20) and orientations. A mechanism by which Al₂O₃ reacts with SiO₂ has been proposed. It has been revealed that sapphire samples with different crystallographic orientations exhibit an anisotropic rate of material removal. The anisotropy can be explained by a difference in the rate of the formation of intermediate products during chemical interaction between aluminum and silicon oxides on different planes.     

Cation Effect on Copper Chemical Mechanical Polishing

We examine the effect of cations in solutions containing benzotriazole （BTA） and H202 on copper chemical mechanical polishing （CMP）. On the base of atomic force microscopy （AFM） and material removal rate （MRR） results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demonstrates the worst performance. These results reveal a mechanism that small molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential （OCP）.     

Damage/ablation morphology of laser conditioned sapphire under 1064 nm laser irradiation

The damage/ablation morphologies and laser induced damage threshold (LIDT) of three different sapphire samples: original, 1064 nm laser conditioned and 10.6 μm CO₂ laser polished substrates are investigated with ns pulses laser irradiation. The results indicate that the damage resistance capability cannot be enhanced by 1064 nm laser conditioning or CO₂ laser polishing. The damage/ablation morphology of 1064 nm-laser conditioned samples is same as that of the original sapphire. But it is different from the damage/ablation morphology of the CO₂ laser polished sapphire. The “gentle and strong” ablation phases are observed in this work and several phenomena are observed in the two ablation phases. Ripple is observed in the “gentle” ablation processes, while convex spots and raised rims are observed in the “strong” ablation processes. Meanwhile, stripe damage and pin-points are observed in the CO₂ laser conditioned sapphire after ns laser irradiation. The formation mechanisms of the phenomena are also discussed for the explanation of related damage/ablation morphology. The results may be helpful for the damage/ablation investigation of sapphire in high power laser systems.     

X-ray properties and interface study of B4C/Mo and B4C/Mo2C periodic multilayers

We present a comparative study of B₄C/Mo and B₄C/Mo₂C periodic multilayer structures deposited by magnetron sputtering. The characterization was performed by grazing incidence X-ray reflectometry at two different energies and high resolution transmission electron microscopy. The experimental results indicate the existence of an interdiffusion layer at the B₄C-on-Mo interface in the B₄C/Mo system. Thus, the B₄C/Mo multilayers were modeled by an asymmetric structure with three layers in each period. The thickness of B₄C-on-Mo interfacial layer was estimated about 1.1 nm. The B₄C/Mo₂C multilayers present less interdiffusion and are well modeled by a symmetric structure without interfacial layers. This study shows that B₄C/Mo₂C structure is an interesting alternative to B₄C/Mo multilayer for X-ray optic applications.     

Structural and morphological characterizations of ZnO films grown on GaAs substrates by MOCVD

The production of boron carbide (B₄C) nanoparticles was investigated in a conventional high temperature furnace reactor. The reaction was carried out by heating a mixture of amorphous carbon and amorphous boron at 1550 °C to efficiently obtain a quantity of B₄C. Scanning electron microscopy studies showed the average size of B₄C particles was 200 nm, ranging from 50 nm to 350 nm. X-ray diffraction transmission electron microscopy and electron diffraction studies indicated that the prepared nanoparticles were crystalline B₄C with a high density twin structure. High resolution transmission electron microscopy and selected area diffraction were also used to further characterize the structure of the prepared B₄C particles, while energy dispersive spectroscopy and electron energy loss spectroscopy were used to determine the stoichiometry of the product. A solid state diffusion reaction mechanism is proposed.     

Growth fusion of submicron spherical boron carbide particles by repetitive pulsed laser irradiation in liquid media

We studied the fabrication of B₄C submicron particles by laser irradiation of boron nanoparticles dispersed in an organic solvent. The spherical shape of the formed particles suggests that instantaneous melt formation and solidification by quenching are involved in the particle-forming process. B₄C particles gradually became larger with irradiation time at relatively low laser fluence (1.5 J cm⁻² pulse⁻¹) by repetitive melting and fusion of the particles, and the B₄C yield increased with irradiation time to 90% for 600 min of irradiation. At higher laser fluences, the B₄C yield decreased due to the explosive ablation of boron or B₄C to form H₃BO₃, and thus only the larger B₄C particles were observed. The dielectric constant of the organic solvent also affected the generated B₄C particle size, probably due to the degree of particle aggregation. Thus, this technique can provide a new approach for fabricating spherical submicron particles of ceramic materials, such as carbides, with simple and safe processes.     

Subsurface defect characterization and laser-induced damage performance of fused silica optics polished with colloidal silica and ceria

This paper mainly focuses on the influence of colloidal silica polishing on the damage performance of fused silica optics. In this paper, nanometer sized colloidal silica and micron sized ceria are used to polish fused silica optics. The colloidal silica polished samples and ceria polished samples exhibit that the root-mean-squared(RMS) average surface roughness values are 0.7 nm and 1.0 nm, respectively. The subsurface defects and damage performance of the polished optics are analyzed and discussed. It is revealed that colloidal silica polishing will introduce much fewer absorptive contaminant elements and subsurface damages especially no trailing indentation fracture. The 355-nm laser damage test reveals that each of the fused silica samples polished with colloidal silica has a much higher damage threshold and lower damage density than ceria polished samples. Colloidal silica polishing is potential in manufacturing high power laser optics.