铜抛光液对片内非均匀性影响的研究

对于低介电常数材料和铜互连结构在低压化学机械抛光中,研发新的抛光液和调整工艺参数是非常必要的。抛光液的研发是减少抛光表面划伤和解决磨料剩余的关键。抛光液组成由片内非均匀性和铜抛光去除速率特性来优化。氧化剂浓度1Vol%;磨料浓度0.8Vol%;螯合剂浓度2Vol%。工作压力1kPa。抛光后表面缺陷减小并且表面干净无污染。去除速率289nm/min,片内非均匀性0.065。化学机械抛光后用原子力测量粗糙度为0.22 nm。     

碱性铜精抛液中表面活性剂ADS对平坦化效果的影响

研究了阴离子表面活性剂十二烷基硫酸铵(ADS)在弱碱性铜抛光液中对晶圆平坦化效果的影响.对不同质量分数的阴离子表面活性剂ADS下的抛光液表面张力、铜去除速率、抛光后铜膜的碟形坑高度、晶圆片内非均匀性和表面粗糙度进行了测试.实验结果表明,当阴离子表面活性剂ADS的质量分数为0.2％时,抛光液的表面张力降低,铜的去除速率为202.5 nm·min-1,去除速率片内非均匀性减小到4.15％,抛光后铜膜的碟形坑高度从132 nm降低到68.9 nm,表面粗糙度减小到1.06 nm.与未添加表面活性剂相比,晶圆表面的平坦化效果得到改善.     

碱性铜抛光液在CMP工艺中的性能评估

研究了一种碱性铜抛光液,其基本组分是硅溶胶磨料、新型FA/O V型螯合剂、非离子表面活性剂和氧化剂(H2O2)。在压力为2 psi(1 psi=6.895 kPa)、抛头转速与抛盘转速分别为97和103 r/min、流量为300 mL/min的条件下,分析了铜膜去除速率随着螯合剂和氧化剂体积分数增加的作用规律。结果表明,加入体积分数2%的螯合剂和体积分数3%的氧化剂时,抛光液具有较好的自钝化能力和较高的铜膜去除速率。同时,研究了工艺参数在抛光过程中对去除速率和片内非均匀性(WIWNU)的影响,平坦化实验的抛光工艺选择压力1.5 psi、抛头和抛盘转速分别为87和93 r/min、流量300 mL/min。实验结果表明:此种抛光液在上述工艺条件下,抛光结束时剩余高低差为63.7 nm,具有较好的平坦化效果,对抛光液商业化提供了参考价值。     

新型碱性抛光液对300mm TaN镀膜片CMP效果评估

TaN由于其良好的性能广泛用于布线铜与介质之间的阻挡层和黏附层.在对直径为300 mm的TaN镀膜片进行化学机械抛光(CMP)后,对比并分析了两种碱性抛光液对TaN去除速率、片内非均匀性、去除速率选择性和表面粗糙度的影响.结果表明,经过自主研发且不合氧化剂的碱性阻挡层抛光液抛光后,TaN的去除速率为40.1 nm/min,片内非均匀性为3.04％,介质、TaN与Cu的去除速率之比为1.69∶1.26∶1,中心、中间以及边缘的表面粗糙度分别为0.371,0.358和0.366 nm.与商用抛光液抛光结果相比,虽然采用自主研发的抛光液抛光的去除速率低,但片内非均匀性以及选择性均满足商用要求,且抛光后TaN表面粗糙度小,易清洗,无颗粒沾污.综合实验结果表明,自主研发的高性能碱性抛光液对TaN镀膜片具有良好的抛光效果,适合工业生产.     

不同表面活性剂对铜互连阻挡层CMP一致性的影响北大核心CSCD

为实现铜互连阻挡层化学机械抛光的高平坦化,研究了阻挡层抛光液中表面活性剂的作用。在抛光液中分别添加非离子型表面活性剂异辛醇聚氧乙烯醚(JFC-E)、本课题组研发的Ⅱ型活性剂以及复合表面活性剂,研究其对阻挡层CMP中铜和正硅酸乙酯(TEOS)去除速率及一致性的影响。实验结果表明,表面活性剂不仅可以改善Cu和TEOS的去除速率一致性和晶圆全局一致性,还可以降低铜表面的粗糙度,通过复配两种不同的表面活性剂,可以提高Cu和TEOS的去除速率,使Cu和TEOS的剩余厚度片内非均匀性(WIWNU)分别降低至1.39%和1.38%,铜表面粗糙度从5.25 nm降至1.51 nm。基于实验结果,研究并提出了表面活性剂影响抛光液润湿性,从而改善片内非均匀性和铜表面质量的机理。     

航空太阳能电池用超薄锗单晶的精密抛光

主要对影响锗单晶抛光后表面微粗糙度的关键因素—抛光液组分的作用进行分析。采用变量控制的实验方法,从活性剂、有机胺碱、氧化剂、硅溶胶磨料和螯合剂五个因素出发进行实验。针对粗糙度影响因素进行分析与优化,同时对抛光速率进行了分析,研究得出,抛光液组分中氧化剂浓度对CMP过程中锗衬底片表面微粗糙度及去除速率的影响最为显著。优化抛光液组分配比,在抛光速率基本满足工业要求(1.5μm/min)下,经过CMP后锗衬底表面微粗糙度可有效降到1.81 nm(10μm×10μm)。在最佳配比下,采用小粒径、低分散度(99%82.2 nm)的硅溶胶磨料配制抛光液,其抛光效果明显优于采用大粒径、高分散度的硅溶胶磨料配制的抛光液。     

一种使用超声波精细雾化施液的SiO2抛光液

使用硅溶胶、pH值调节剂、表面活性剂和氧化剂等组分配制抛光液,通过超声波发生器雾化后,在负压下导入抛光区域界面进行CMP实验,并在相同的抛光参数下,与SSP-L抛光液常规抛光进行了比较。结果表明:当磨粒质量分数为20%、pH值为11、表面活性剂和氧化剂的质量分数分别为0.5%和2%时,材料去除率MRR达到490 nm/min,表面粗糙度Ra为2.72 nm。配制的抛光液的雾化抛光效果和SSP-L抛光液常规抛光效果接近,而雾化抛光液用量接近常规抛光液的1/10。分析原因是雾化液均匀的化学组分以及在界面化学反应中的高活性、强吸附性,有利于材料去除和形成超精细的表面。     

非离子表面活性剂在钽基阻挡层CMP中的作用

碱性条件下,非离子型表面活性剂在阻挡层化学机械平坦化中起着重要的作用。分别对阻挡层材料Cu、Ta以及SiO₂介质进行抛光,然后测量铜表面粗糙度。对含有不同浓度活性剂的抛光液进行接触角和Zeta电位的测试,并对活性剂的作用机理进行分析。活性剂体积分数达到3%时,铜表面粗糙度可达0.679 nm,抛光液在铜膜表面的接触角低至10.25°,Zeta电位达到-50.2 mV。实验结果表明,活性剂在减小粗糙度的同时可提高抛光液的湿润性和稳定性,便于抛光后清洗和长时间放置。     

CMP抛光液对TiO_2薄膜表面粗糙度的影响北大核心CSCD

采用自主配制的碱性抛光液对TiO2薄膜进行了化学机械抛光(CMP),研究了在TiO2薄膜CMP加工过程中,碱性抛光液中的SiO2磨料、螯合剂、表面活性剂的体积分数和抛光液pH值对TiO2薄膜表面粗糙度的影响,并进行了参数优化。实验结果表明,在一定的抛光条件下,选用SiO2磨料体积分数为20%、螯合剂体积分数为1.0%、非离子表面活性剂体积分数为5.0%和pH值为9.0的碱性抛光液,抛光后TiO2薄膜表面没有划痕等抛光缺陷,表面粗糙度为0.308 nm,TiO2薄膜去除速率为24 nm/min,在保证抛光速率的同时降低了TiO2薄膜表面粗糙度,满足工业化生产要求。     

CMP抛光液对TiO2薄膜表面粗糙度的影响

采用自主配制的碱性抛光液对TiO2薄膜进行了化学机械抛光(CMP),研究了在TiO2薄膜CMP加工过程中,碱性抛光液中的SiO2磨料、螯合剂、表面活性剂的体积分数和抛光液pH值对TiO2薄膜表面粗糙度的影响,并进行了参数优化。实验结果表明,在一定的抛光条件下,选用SiO2磨料体积分数为20%、螯合剂体积分数为1.0%、非离子表面活性剂体积分数为5.0%和pH值为9.0的碱性抛光液,抛光后TiO2薄膜表面没有划痕等抛光缺陷,表面粗糙度为0.308 nm,TiO2薄膜去除速率为24 nm/min,在保证抛光速率的同时降低了TiO2薄膜表面粗糙度,满足工业化生产要求。     

弱碱性抛光液中FA/O 螯合剂和H2O2对Ru CMP的影响研究

Ru作为一种新型阻挡层材料已经应用到了先进的集成电路生产中。但由于金属钌特殊的物理化学性质使其化学机械抛光(CMP)还存在很多问题。为了提高Ru的去除速率,本文研究了FA/O螯合剂和H2O2对Ru的抛光去除速率(RR)和静态腐蚀速率(SER)的影响。实验结果表明,随着H2O2浓度的增加,在抛光过程中,Ru表面形成了致密氧化层,导致Ru的抛光去除速率(RR)和静态腐蚀速率(SER)先增加后减少。通过电化学方法对Ru表面的腐蚀情况进行了分析研究。结果表明,FA/O螯合剂能通过与Ru的氧化物((RuO4)2- 和RuO4 )形成可溶性胺盐([R(NH3)4] (RuO4)2) 提高Ru 的去除速率。同时,为了降低金属Ru CMP后表面粗糙度,在抛光液中加入了非离子表面活性剂AD。     

硫化铵钝化锑化镓表面的化学与电学性质研究

本文利用X射线光电子能谱（XPS）,飞行时间二次离子质谱（TOF-SIMS）和电流-电压特性（I-V）对不同硫化铵溶液（(NH4)2S）钝化后的锑化镓（GaSb）表面化学性质进行了研究。通过对比,发现中性(NH4)2S S溶液对GaSb表面的钝化能力要优于纯(NH4)2S溶液和碱性(NH4)2S S溶液。碱性(NH4)2S S溶液在有效去除GaSb表面氧化物的同时形成硫化物产物以改善器件性能。TOF-SIMS测试结果从另一方面证实纯(NH4)2S溶液钝化也会形成硫化物产物,但该产物在纯(NH4)2S溶液中是可溶的,以至于很难稳定地存在。3D光学轮廓仪测试结果显示中性(NH4)2S S溶液钝化的GaSb表面具有最低的粗糙度。I-V测试结果表明中性(NH4)2S S溶液钝化能显著提高GaSb基肖特基二极管的电学性能。综上所述,中性(NH4)2S S溶液的钝化效果在改进GaSb表面性质方面具有最优的结果。     

不同压力下螯合剂浓度在碱性Cu CMP中的影响

We propose the action mechanism of Cu chemical mechanical planarization(CMP) in an alkaline solution.Meanwhile,the effect of abrasive mass fraction on the copper removal rate and within wafer non-uniformity(WIWNU) have been researched.In addition,we have also investigated the synergistic effect between the applied pressure and the FA/O chelating agent on the copper removal rate and WIWNU in the CMP process.Based on the experimental results,we chose several concentrations of the FA/O chelating agent,which added in the slurry can obtain a relatively high removal rate and a low WIWNU after polishing,to investigate the planarization performance of the copper slurry under different applied pressure conditions.The results demonstrate that the copper removal rate can reach 6125 °/min when the abrasive concentration is 3 wt.%.From the planarization experimental results,we can see that the residual step height is 562 ° after excessive copper of the wafer surface is eliminated.It denotes that a good polishing result is acquired when the FA/O chelating agent concentration and applied pressure are fixed at 3 vol% and 1 psi,respectively.All the results set forth here are very valuable for the research and development of alkaline slurry.     

Abrasive-Free Chemical Mechanical Polishing of Hard Disk Substrate with Cumene Hydroperoxide-H2O2 Slurry

With magnetic heads operating closer to hard disks, the hard disks must be ultra-smooth. The abrasive-free polishing (AFP) performance of cumene hydroperoxide (CHP) as the initiator in H₂O₂-based slurry for hard disk substrate was investigated in our work, and the results showed that the slurry including CHP could improve the material removal rate (MRR) and also reduce surface roughness. Electron spin-resonance spectroscopy (EPR), electrochemical measurement and Auger electron spectroscopy (AES) were conducted to investigate the acting mechanism with CHP during the polishing process. Compared with the H₂O₂ slurry, the EPR analysis shows that the CHP–H₂O₂ slurry provides a higher concentration of the HO^O free radical. In addition, the AES analysis shows the oxidization reaction occurs in the external layer of the substrate surface. Furthermore, electrochemical measurements reveal that CHP can promote the electrochemical effect in AFP and lead to the increase of MRR.     

Optimization of slurry components for a copper chemical mechanical polishing at low down pressure using response surface methodology

Copper replaced aluminium and the low-dielectric constant material (low-k dielectrics) served as a better isolator, which has become the inevitable developing trend of IC technology. Due to the low compression resistance of low-k material, the mechanical strength must be reduced in order to ensure the functional integrity, which is a challenge for the traditional chemical-mechanical polishing (CMP) technology. To solve this issue, it is necessary to develop a chemically dominant CMP process at low down pressure. It is generally known that the implementation of optimum slurry composition is one of the important issues. To achieve a high removal rate (RR) and minimal WIWNU (Within-Wafer Non-Uniformity) at a down pressure of 0.63 psi, the response surface methodology (RSM) was applied to optimize slurry composition which contains silica sols, H₂O₂ and FA/O chelating agent. A central composite design, which is the standard design of RSM, was used to evaluate the effects and interactions of three factors. The optimal conditions obtained from the compromise of the two desirable responses, RR and WIWNU, were silica sols concentration of 13.88 vol.%, H₂O₂ concentration of 16.13 ml/L and FA/O chelating agent concentration of 20.22 ml/L, respectively. The RSM was demonstrated as an appropriate approach for the optimization of the slurry components by confirmation experiments.     

Achievement of high planarization efficiency in CMP of copper at a reduced down pressure

We report improved planarization efficiency (ratio of step height reduction and removed layer thickness) in chemical-mechanical planarization (CMP) of copper lines at a down pressure of 2 psi. The CMP slurry used to achieve these results contains fumed silica particles (abrasive), β-alanine (surface complexing agent) and H₂O₂ (oxidizer), combined with dissolution inhibiting ammonium dodecyl sulfate (ADS) and/or low concentrations (≤1 mM) of benzotriazole (BTAH) at a solution pH of 4.0. When only ADS or BTAH is used, Cu dissolution rate is reduced, but at the cost of somewhat low planarization efficiency. Combination of ADS (typically 3 mM) and BTAH (≤1 mM) in the slurry significantly improves both the surface polish rates and the planarization efficiency. The processed surface (examined by optical profilometry) is noticeably defect-free for this particular system. The mechanisms of surface dissolution and passivation are discussed, and contact angle data are used to elucidate the surface passivating nature of the inhibitor films. The results presented here are relevant for further developments in the area of low pressure CMP of Cu lines overlying fragile low-k dielectrics in the new interconnect structures.     

Effects of surface passivation during atomic layer deposition of Al2O3 on In0.53Ga0.47As substrates

In this work we investigate the effect of different III-V surface passivation strategies during atomic layer deposition of Al₂O₃. X-ray photoelectron spectroscopy indicates that bare As-decapped and sulfur passivated In_0.53Ga_0.47As present residual oxides on the surface just before the beginning of the Al₂O₃ deposition while the insertion of a Ge interface passivation layer results in an almost oxide free Ge/III-V interface. The study of the initial growth regimes, by means of in situ spectroscopic ellipsometry, shows that the growth of Al₂O₃ on Ge leads to an enhanced initial growth accompanied by the formation of Ge-O-Al species thus affecting the final electrical properties of the stack. Alternatively, deposition on decapped and S-passivated In_0.53Ga_0.47As results in a more controlled growth process. The sulfur passivation leads to a better electrical response of the capacitor that can be associated to a lower oxide/semiconductor interface trap density.     

Effective passivation of defects in Ge-rich SiGe-on-insulator substrates by Al2O3 deposition and subsequent post-annealing

A method of Al₂O₃ deposition and subsequent post-deposition annealing (Al₂O₃-PDA) was proposed to passivate electrically active defects in Ge-rich SiGe-on-insulator (SGOI) substrates, which were fabricated using Ge condensation by dry oxidation. The effect of Al₂O₃-PDA on defect passivation was clarified by surface analysis and electrical evaluation. It was found that Al₂O₃-PDA could not only suppress the surface reaction during Al-PDA in our previous work [Yang H, Wang D, Nakashima H, Hirayama K, Kojima S, Ikeura S. Defect control by Al-deposition and the subsequent post-annealing for SiGe-on-insulator substrates with different Ge fractions. Thin Solid Films 2010; 518: 2342-5.], but could also effectively passivate p-type defects generated during Ge condensation. The concentration in the range of 10¹⁶-10¹⁸ cm⁻³ for defect-induced acceptors and holes in Ge-rich SGOI drastically decreased after Al₂O₃-PDA. As a result of defect passivation, the electrical characteristics of both back-gate p-channel and n-channel metal-oxide-semiconductor field-effect transistors fabricated on Ge-rich SGOI were greatly improved after Al₂O₃-PDA.     

原子层沉积氧化铝薄膜对多晶太阳能电池表面钝化的影响

A stack of Al2O3/SiNx dual layer was applied for the back side surface passivation of p-type multi-crystalline silicon solar cells, with laser-opened line metal contacts, forming a local aluminum back surface field （local Al-BSF） structure. A slight amount of Al2O3, wrapping around to the front side of the wafer during the thermal atomic layer deposition process, was found to have a negative influence on cell performance. The different process flow was found to lead to a different cell performance, because of the Al2O3 wrapping around the front surface. The best cell performance, with an absolute efficiency gain of about 0.6% compared with the normal full Al-BSF structure solar cell, was achieved when the Al2O3 layer was deposited after the front surface of the wafer had been covered by a SiNx layer. We discuss the possible reasons for this phenomenon, and propose three explanations as the Ag paste, being hindered from firing through the front passivation layer, degraded the SiNx passivation effect and the Al2O3 induced an inversion effect on the front surface. Characterization methods like internal quantum efficiency and contact resistance scanning were used to assist our understanding of the underlying mechanisms.     

非离子型活性剂在ULSI碱性Cu抛光液中的性能

使用四种非离子表面活性剂分别添加到以SiO2水溶胶为磨料、H2O2为氧化剂的碱性Cu抛光液中进行抛光实验.结果表明,所选用的非离子型表面活性剂对材料去除率的影响不大,当烷基酚聚氧乙烯醚在质量分数为0.25%时,抛光表面质量提高,表面粗糙度(Ra)由1.354 nm下降到了0.897 6 nm,同时有效地减轻了Cu抛光表面的划痕和腐蚀,其原因是聚氧乙烯链可以通过醚键与水分子形成氢键,在聚氧乙烯周围形成一层溶剂化的水膜保护了被吸附表面.