半导体用高纯钨靶材的制备技术与应用

难熔金属钨及钨合金由于具有高温稳定性好、电子迁移抗力高以及电子发射系数高等优点,在半导体大规模集成电路制造过程中有着广泛的应用。本文对半导体用高纯钨及钨合金靶材的应用领域、性能要求以及制备方法进行了详细的分析,并对其发展趋势进行了展望。高纯钨及钨合金靶材主要用于制造半导体集成电路的栅电极、连接布线、扩散阻挡层等,对材料的纯度、杂质元素含量、致密度、晶粒尺寸及晶粒组织均匀性等方面都有着极高的要求。高纯钨及钨合金靶材主要采用热压、热等静压等方式来制备,采用中频烧结+压力加工的方式可以制备出高纯度、高致密度的钨靶材,但晶粒尺寸及晶粒组织均匀性控制方面,与热等静压制备的钨靶仍有一定的差距。     

磁控溅射用难熔金属靶材制作、应用与发展

随着磁控溅射技术应用日益广泛,难熔金属靶材需求不断增大。就难熔金属靶材应用、制备及发展进行总结和探讨,分析了制作过程中致密度、纯度、晶粒尺寸及结晶取向对靶材性能的影响,并对难熔金属靶材的发展趋势进行展望。     

粉末冶金制备TiAl基合金板材的研究现状及趋势

综述了TiAl基合金板材的元素粉法和预合金粉法2种粉末冶金制备工艺，介绍了元素粉末法、金属箔片法、预合金粉热轧法、物理气相沉积法和等离子喷涂法等工艺的制备过程和材料性能，论述了上述方法的特点和发展趋势。     

脉冲激光沉积镀膜工艺中不同靶材制备方法对La_(0.72)Ca_(0.28)MnO_3薄膜电学性能和激光感生电压的影响（英文）

采用脉冲激光沉积方法在单晶LaAlO3(100)平衬底和15°倾斜衬底上制备La0.72Ca0.28MnO3薄膜。在镀膜过程中分别采用溶胶-凝胶法和共沉淀法制备靶材。研究不同方法制备的靶材和相应的薄膜的结构、电输运性能和表面形貌。与共沉淀法相比,采用溶胶-凝胶法制备的靶材具有更加均匀的组分和更大的致密度以及晶粒尺寸,因此具有更高的绝缘体-金属转变温度和更大的电阻温度系数。采用溶胶-凝胶靶材制备的薄膜,其晶粒尺寸更均匀、生长质量更好,绝缘体-金属转变温度高20 K,激光感生电压也更大。因此,使用溶胶-凝胶方法制备靶材可以大幅提高脉冲激光沉积方法中薄膜的性能。     

铜溅射靶及铜合金溅射靶的制备方法

高纯度铜溅射靶及铜合金溅射靶现在被用于多种用途,例如集成电路的制造。含铜结构的例如相互连接及薄膜的品质依赖于靶材的溅射性能。作为影响靶的溅射性能的因素,可列举：靶材的平均晶粒度及晶粒度均匀性、靶材的结晶／组织、靶材内部的结构上及组成上的均质性、以及靶材的强度。     

反应等离子喷涂 TiN 涂层的研究进展

TiN具有硬度高、韧性好、摩擦系数小、化学性能稳定等优点,广泛应用于刀具、装饰、表面防护等领域。目前制备TiN涂层的方法有很多,如气相沉积、热喷涂、电镀等,反应等离子喷涂则是最常用的金属-陶瓷复合涂层制备方法。概述了反应等离子喷涂技术的基本原理和分类,包括反应等离子喷涂涂层的形成过程及工艺的优缺点。综述了反应等离子喷涂TiN涂层的喷涂工艺及性能的研究进展,包括涂层的制备方法(原位合成法、烧结破碎法)和性能特点,重点分析了涂层的力学性能、耐磨损性能、耐腐蚀性能,并提出了可以依靠热处理工艺或封孔技术来提高涂层的耐腐蚀性能。依据实验和查阅的文献,反应等离子喷涂结合了自蔓延高温合成技术和等离子喷涂技术,可以制备质量优良的厚TiN涂层(500μm),是一种新型的低成本涂层制备技术,但是反应等离子喷涂制备TiN涂层存在孔隙率较高(5%~10%)、结合强度较低(50 MPa)的问题。分别从技术、设备、工艺、后处理四个方面总结了改善涂层质量的相应措施,展望了今后的研究发展方向。     

粉末冶金靶材多弧离子镀HY3涂层抗氧化性能

目的 研究靶材制备工艺对多弧离子镀(Arc ion plating,AIP)MCrAlY涂层抗氧化性能的影响。方法 采用粉末冶金方法制备NiCrAlYSi(HY3)靶材,然后采用AIP在DZ125合金基体上制备HY3涂层。在1 100 ℃下对粉末冶金靶材制备涂层进行200 h的静态氧化实验,采用SEM、XRD等对靶材和氧化前后的涂层进行微观组织分析,并与传统铸造靶材进行对比。结果 采用粉末冶金方法制备的靶材成分更加均匀,相尺寸约为5 μm,相较于铸造靶材降低了1个数量级。采用粉末冶金靶材制备的涂层(P涂层)元素分布更均匀、β相含量更高。经过1 100 ℃、200 h的高温氧化,P涂层的氧化增量为1.01 mg/cm²,低于铸造靶材制备的涂层(C涂层,1.10 mg/cm²)。在200 h后,P涂层表面的热生长氧化物(TGO)完整,而C涂层表面的TGO出现了剥落现象,P涂层的活性元素均匀分布,促进TGO内生成了少量弥散分布的钉扎氧化物Y2Hf2O7,提高了TGO的抗剥落能力。更高的β相含量促进了氧化初期θ−Al2O3的快速生成,有利于P涂层生成保护性能更好的TGO。结论 粉末冶金靶材成分的均匀性优于传统铸造靶材,采用粉末冶金靶材制备的HY3涂层的抗高温氧化性能优于铸造靶材制备的HY3涂层。     

镍酸镧陶瓷靶材的制备工艺北大核心CSCD

采用固相反应法制备镍酸镧(LaNiO3)粉体,利用常压烧结法烧结LaNiO3陶瓷靶材。探索了制备LaNiO3陶瓷粉体的工艺条件;利用X射线衍射(XRD)和扫描电镜(SEM)分析了固相反应热处理工艺及烧结工艺对LaNiO3陶瓷粉体及靶材的相组成及微观形貌的影响。结果表明:在氧气气氛中,900℃下煅烧10 h可获得纯度较高、晶粒细小的LaNiO3粉体;烧结温度为1100℃保温4 h时,获得了比较致密且晶粒分布均匀的LaNiO3陶瓷靶材,同时电阻率达到了0.52 mΩ·cm。     

纳米Al_2O_3对等离子喷涂ZrC-ZrSi_2复合涂层结构与性能的影响

大气等离子喷涂ZrC-ZrSi_2陶瓷涂层的孔隙率高,提高等离子喷涂ZrC-ZrSi_2陶瓷涂层的致密度成为亟待解决的问题。在TC4钛合金表面采用大气等离子喷涂ZrC-ZrSi_2复合粉和ZrC-ZrSi_2-Al_2O_3复合粉分别制备两种复合涂层。研究纳米Al_2O_3对等离子喷涂ZrC-ZrSi_2复合涂层组织结构与性能的影响。结果表明,添加了Al_2O_3的ZrC-ZrSi_2复合涂层的组织结构更为致密,相较于ZrC-ZrSi_2复合涂层具有更优异的力学性能。熔点相对较低的Al_2O_3能够在喷涂焰流中先熔化,熔融态的Al_2O_3能够填充在ZrC-ZrSi_2复合涂层的孔洞处,提高复合涂层的致密度,改善涂层的力学性能。研究成果可为提高大气等离子喷涂制备含高熔点组分复合涂层的致密度提供指导。     

难熔金属钨、钼管材的应用及其制备技术研究进展

近年来,难熔金属W、Mo管材因其高熔点、高强度、热膨胀系数低、电阻率低、良好的热稳定性等优点被广泛应用于溅射镀膜行业、航空航天以及核工业领域。本文从难熔金属W、Mo管材的应用着手,重点分析了目前常用的W、Mo管材的制备方法,包括挤压、锻造、旋压、热等静压、等离子喷涂、化学气相沉积(CVD)等的工艺特点、管材性能优势及应用方向,提出了今后难熔金属W、Mo管材技术研发方向。应用于平面显示、太阳能光伏等行业的大尺寸高纯Mo及Mo合金管状溅射靶材,是难熔金属W、Mo材料最为重要的高端应用发展方向;我国在大尺寸W、Mo及其合金管靶制备等方面需进一步加强相关基础研究工作与装备投入。     

Manufacture and properties of cold spray deposited large thickness Cu coating material for sputtering target

In this study, the manufacture of a large thickness Cu coating layer as sputtering target material via a cold spray coating process was undertaken. The microstructure and properties of the Cu layer as the sputtering target material (before and after the annealing heat treatment) were evaluated, compared, and analyzed. To evaluate the purity, density, grain size and uniformity, microstructure, and properties of the Cu-coated layer as a sputtering target, X-ray diffraction, ICP analysis, SEM, EBSD, porosity analysis, and Vickers hardness tests were performed. The result of the observation of the layer’s purity and microstructure showed that a purity level (99.47%) similar to that of the early powder 2N5 was maintained and that the manufacture of a cold spray deposited, ∼20 mm thick Cu coating material for the sputtering target was performed successfully. As a result of the EBSD mapping, the average grain size near the interface and around the center measured 1.48 μm and 1.49 μm; the grains were small and non-uniform compared with the 1.91 μm size near the surface. Note, however, that the recrystallization and grain growth (caused by annealing) increased the grain size to 1.82 μm (near the interface), 1.83 μm (near the center), and 1.87 μm (near the surface) and improved the level of uniformity. Moreover, through post heat treatment, the overall porosity declined (0.44 % porosity/400 °C/h heat treatment), and the grain texture became uniform. The possibility of controlling the microstructure as a large thickness sputtering target by conducting an annealing heat treatment was also confirmed. Nonetheless, the differences in the porosity and hardness associated with the coating thickness changes were partially maintained. Based on the aforementioned findings, this study suggests that by using cold spray deposition, Cu coating layers with large thicknesses can be applied as a sputtering target.     

双级HPPMS靶电流对TiN镀层微观结构及耐蚀性的影响

高功率脉冲磁控溅射（HPPMS）利用较高的脉冲峰值靶功率密度（如：1-3kW/cm2）获得高密度的等离子体,可提高TiN镀层的微观结构和力学性能。然而,HPPMS技术的主要缺点是平均沉积速率较低,增加了镀层的制备成本。为了解决传统HPPMS平均沉积速率低的问题,研究提出一种新型的双级HPPMS技术,即在一个脉冲周期内具有两个连续的、独立可调的脉冲阶段。通过对双级HPPMS电场的合理调配,可制备得到结构致密的TiN镀层,研究了双级HPPMS靶电流对TiN镀层微观结构及耐蚀性的影响。结果表明,当靶电流增大至20A时,靶面形貌由小凹坑转变为大面积凹坑,说明镀料粒子的脱靶方式由碰撞溅射转变为升华或蒸发。同时,当靶电流为10A时,镀层颗粒呈现三棱锥状结构,平均晶粒尺寸为11nm;当靶电流增大至25A时,镀层颗粒呈现光滑致密的圆胞状结构,平均晶粒尺寸为18nm,光滑致密的组织结构使镀层具有较好的耐蚀性。     

Comparing Microstructures of ITO Sputtering Targets Prepared by Tin Doped Indium Oxide Powders and In2O3- SnO2 Mixed Powders

磁控溅射ITO靶材制备ITO透明导电薄膜作为平板显示、太阳能电池、气敏元件等电子器件的电极材料,需要ITO靶材具有高纯度、高均匀性、高密度、高导电性的特点。对比研究了ITO共沉淀粉与In2O3、SnO2单体混合粉同炉烧结ITO靶材的微观组织结构差异,如：晶粒尺寸分布、晶粒形貌、元素分布、烧结速率等。结果表明：单体混合粉的烧结速率要比共沉淀粉的烧结速率高,但是前者烧结ITO靶材的微观组织结构不及后者烧结的均匀性好。对比而言,共沉淀粉更容易获得结构组织均匀的ITO靶材,但前提是要合理的设计烧结工艺抑制烧结过程中In2O3的分解。研究结果将会对提高ITO靶材微观组织均匀性和减少靶材毒化,进而提高靶材生产效率提供有益的参考     

粉末冶金W/Re合金靶材的显微结构及磁控溅射沉积性能

为了研制高品质W/Re合金靶材,采用机械混料、压制成形和真空烧结致密化工艺路线制备了纯钨及铼含量分别为1%、5%、10%(质量分数)的钨/铼(W/Re)合金,测试了W/Re合金的致密度、晶粒度及晶粒取向、磁控溅射沉积等性能。研究表明,W/Re合金致密度及纯度均随Re含量增加而逐渐提高,而晶粒逐渐细化。W/10%Re合金靶材晶粒尺寸主要介于10~40μm之间,W/Re合金晶粒随机分布,并未出现明显的择优取向,且其中小角度晶界(<10o)达85%以上,非常适用于磁控溅射镀膜。随着磁控溅射沉积压力的提高,W/Re合金薄膜的晶粒尺寸逐渐细化,镀膜表面平整程度逐渐提高,薄膜的厚度呈逐渐增加的趋势。镀膜在40.5o、58.6o、73.5o附近出现分别属(110)、(200)和(211)晶面的衍射峰,且随着沉积压力的升高,(110)晶面衍射峰逐渐减弱,而(200)晶面衍射峰则稍有增强。纯W靶材由于致密度及纯度偏低,而且晶粒较粗大,无法磁控溅射出完整理想的薄膜。     

Study on the microstructures,electrical resistance and mechanical properties of sputtering chromium target by HP,HIP and canning–HIP processes

In recent years, pure chromium (Cr) targets have been commonly used in metal surface coating treatment and flat-panel displays. In the traditional production of a pure Cr-target, there is a greater use of casting methods; however, the metal ingot frequently suffers from ingredient segregation, porosity and non-uniform microstructure defects. Powder metallurgy (PM) is a good method for fabricating high melting materials with better microstructure and properties. This study produced Cr targets using hot pressing (HP), hot isostatic pressing (HIP) and canning–HIP of PM technology. The experimental results showed that the Cr targets made by HP–HIP can further improve the density and mechanical properties. The relative density increases from 98.8% to 99.3%. Canning–HIP of the Cr target, in particular, can provide smaller grain size (50 μm), lower porosity about 0.3%, and increased relative density to 99.7%, with a TRS of up to 58 MPa. The canning–HIP process also shows the optimal electrical resistivity (8.003 × 10^− 5 Ω-cm), which suits for applications in the sputtering process.     

Microstructure and magnetron sputtering properties of tungsten target fabricated by low pressure plasma spraying

Planar and rotary tungsten targets were fabricated by low pressure plasma spraying (LPPS). Relative density, oxygen content by mass, microstructure, micro-hardness and ultimate tensile strength (UTS) of LPPS tungsten targets were all influenced by vacuum pressure. Compared with 1.3 × 10⁴ Pa and 6.5 × 10⁴ Pa, a vacuum pressure of 3.9 × 10⁴ Pa was optimal for preparing high-quality tungsten targets. Oxygen content by mass, porosity, average grain size, micro-hardness and UTS of LPPS target fabricated under 3.9 × 10⁴ Pa were about 0.18%, 2.8%, 0.9 μm, 377.8HV_0.025 and 201.1 MPa, respectively. Electron backscattered diffraction (EBSD) from the LPPS sample (fabricated under 3.9 × 10⁴ Pa) showed that proportions of 〈001〉, 〈011〉 and 〈111〉 oriented grains were 10.6%, 21.0% and 12.3% of the total, respectively. The tungsten target possessed excellent magnetron sputtering performance since most tungsten grains with a size <1.0 μm were irregularly distributed without preferred orientation. Rapid sputtering and uniform thinning on the surface of LPPS tungsten targets took place with nano-scaled sputtering pits being formed during magnetron sputtering. Smooth and continuous tungsten thin films with thickness about 320 nm can be deposited by magnetron sputtering from the LPPS samples. XRD spectra of tungsten thin films with body centered cubic structure showed that the intensity of the (110) diffraction peak was much higher than those of the (200), (211) and (220) peaks.     

钌粉提纯和钌靶制备的研究进展

钌靶在电子信息行业中具有重要的应用价值，我国的钌靶制备技术与国外相比尚存在一定差距。综述了钌提纯中传统提纯工艺和新提纯工艺的特点。对比了热压(HP)、直接热压(DHP)和放电等离子烧结(SPS)等不同工艺加工所得钌靶的差异。分析了靶材的纯度、密度、晶粒大小、晶面取向、成分和组织的均匀性等特性对溅射薄膜的影响。探讨了高品质钌靶的制约因素和发展方向。     

Manufacturing and Macroscopic Properties of Cold Sprayed Cu-In Coating Material for Sputtering Target

This study attempted to manufacture a Cu-In coating layer via the cold spray process and to investigate the applicability of the layer as a sputtering target material. In addition, changes made to the microstructure and properties of the layer due to annealing heat treatment were evaluated, compared, and analyzed. To examine the microstructural and property changes made to the Cu-In coating layer and Cu coating layer (comparison material), ICP, XRD, SEM, and other tests were conducted; purity, density, hardness, porosity, and bond-strength were measured. The results showed that coating layers with thickness of 20 mm (Cu) and 810 μm (Cu-In) could be manufactured via cold spraying under optimal process conditions. With the Cu-In coating layer, the pure Cu and intermetallic compounds of Cu₇In₃ and CuIn₄ were found to exist inside the layer regardless of annealing heat treatment. The preannealing inconsistent microstructure of the layer, whose phases were difficult to distinguish was found to have transformed into one with clearer phase distinction and fine, consistent grains following thermal treatment via a progress of recovery, recrystallization, and grain growth. The porosity and hardness values of the coating layers were 1.4% and 133.9 HV, respectively, for Cu and 3.54% and 476.6 HV, respectively, for Cu-In. The values of the Cu-In layer were higher than those of the Cu layer in terms of porosity and hardness, which declined drastically after annealing. With the porosity of the Cu-In coating layer in particular, the higher value found during the preannealing stage dropped to 0.36% after heat treatment of 773 K/1 h as the level on a par with pure Cu (0.44%), thus indicating the improved quality of the Cu-In layer. Moreover, the results of the bond-strength measurement performed on the Cu-In coating layer and annealing treated materials revealed the strength to be relatively high for heat treated coating layers. Based on the findings of this study and on the comparison and discussion of the properties that are typically required of the target material, the Cu-In coating layer manufactured via cold spray process and annealing heat treatment can be said to be applicable as sputtering target in the future.     

磁控溅射铜靶晶粒度对溅射性能与沉积性能的影响

将平均晶粒度分别为30、70和150 μm的3块6N高纯纯铜方靶放在同一溅射系统中进行溅射,并检测和观察溅射后I-V特征曲线、质量损失以及所镀薄膜的表面形貌、厚度以及X射线衍射谱。结果表明,晶粒度作为靶材的一个重要参数指标,会影响靶材溅射后表面形貌和I-V特性曲线。当所镀薄膜较厚时,靶晶粒度并不会对靶的质量损失以及薄膜结晶情况产生太大的影响,但会对薄膜沉积率产生较大影响。     

超音速大气等离子喷涂TiB2−SiC涂层的制备与性能

将喷雾造粒制备的TiB2?SiC粉末进行真空煅烧,采用超音速大气等离子喷涂制备TiB2?SiC涂层,研究喷涂功率和喷涂距离对TiB2?SiC涂层性能的影响,并对超音速等离子喷涂制备TiB2?SiC涂层的工艺进行优化.结果表明:煅烧后的喷涂粉末粒径分布均匀,球形度良好,流动性增强.煅烧粉末制备的涂层结构致密、沉积效率高....