锗的添加对磁控溅射技术制备的氮化钛薄膜的形态和性能的影响
Abstract: Thin films of TM– X– N (TM stands for early transition metal and X = Si, Al, etc.) are used as protective coatings. The most investigated among the ternary composite systems is Ti– Si– N. The system Ti– Ge – N has been chosen to extend the knowledge about the formation of nanocomposite films. Ti– Ge – N thin films were deposited by reactive magnetron sputtering on Si and WC– Co substrates atTs= 240-C, from confocal Ti and Ge targets in mixed Ar/N2atmosphere. The nitrogen partial pressure and the power on the Ti target were kept constant, while the power on the Ge target was varied in order to obtain various Ge concentrations in the films. No presence of Ge – N bonds was detected, while Xray photoelectron spectroscopy measurements revealed the presence of Ti– Ge bonds. Transmission Electron Microscopy investigations have shown important changes induced by Ge addition in the morphology and structure of Ti– Ge – N films. Electron Energy-Loss Spectrometry study revealed a significant increase of Ge content at the grain boundaries. The segregation of Ge atoms to the TiN crystallite surface appears to be responsible for limitation of crystal growth and formation of a TiGe y amorphous phase
摘要:TM- X-N的薄膜(TM代表前过渡金属,X =硅,铝等)被用作保护涂层。三元复合体系中研究最多的为Ti -SI- N的系统钛锗 ​​- N的已被选定为延续约纳米复合膜的形成的知识。钛锗 - N的薄膜,通过在Si和WC-Co硬质合金反应磁控溅射沉积基板ATTS = 240 -C ,从混合Ar/N2atmosphere共聚焦钛和锗的目标。的氮分压和在Ti靶的功率保持恒定,同时对Ge靶的功率是变化的,以便获得各种的Ge浓度的膜。检测N键,而X射线光电子能谱测量揭示的Ti- Ge键的存在 - 葛没有出现。透射电子显微镜的调查已经表明,在钛锗的形态和结构由葛除了引起重要的变化 - N薄膜。电子能量损失光谱法研究发现Ge含量在晶界显著增加。 Ge原子的氮化钛晶粒表面的偏析似乎是负责晶体生长一个总IgE Ý非晶相的形成和限制
reactor 性能
1、Introduction
Due to their mechanical properties, high melting point and high chemical and thermodynamic stability, transition metal nitrides are attractive materials for various technological applications such as protective coating in industry, diffusion barrier or tunnel junctions in microelectronics, and hard coating in machining tools. The improvement of a particular film property (e.g. hardness, chemical inertness) can be achieved by addition of a
third element (e.g. Al, B, Cr, Si) to a binary nitride (e.g. TiN, ZrN, NbN, CrN) for obtaining a ternary compound [1– 10]. Even in small quantity this third element plays a decisive role in the modification of chemical bonding, structure and morphology.
由于它们的机械性能,高的熔点和高的化学和热稳定性,过渡金属氮化物是各种技术应用,例如保护性涂层在工业,在微电子扩散阻挡层或隧道结,并且在加工工具的硬质被膜有吸引力的材料。一个特定的膜特性的提高(例如,硬度,化学惰性)可以通过另外的第三元件(例如铝,硼,铬,硅)的一个二进制氮化物(如氮化钛,氮化锆, NbN等,氮化铬)用于获得实现三元化合物[1 - 10 ] 。即使在少量第三元素化学键合,结构和形态的改造起着决定性的作用。
Nanocomposite coatings are composed of nanocrystallites of stable transition metal nitride and a ductile metal (Cu, Ni,etc.) [7,11 –14] or a stable nonmetallic nitride phase (SiNx ,BNx, AlN, etc.) [1– 6,9,15]. They can be deposited by various techniques in order to obtain multiphase systems. In this type of materials the macroscopic properties (e.g. electrical conductivity, strength or hardness) are influenced by the microscopic properties of the films as morphology, chemical bonding and local composition.
纳米复合涂料是由稳定的过渡金属氮化物和韧性金属(铜,镍等)纳米晶[ 7,11 -14 ]或稳定的非金属氮化物相(氮化硅, BNX ,氮化铝,等) [ 1 - 6 , 9,15 ] 。它们可以通过各种技术,以便获得多相系统中进行沉积。在这种类型的材料的宏观性质(如导电性,强度或硬度)是由膜的形态,化学粘合和局部组合物的微观特性的影响。
    A new system, Ti–Ge–N, has been chosen to extend the knowledge on ternary multiphase nitride films. Ge is in the group IV of the periodic table like Si. Nevertheless, the chemical reactivity of germanium with nitrogen is significantly lower than that of Si and Ti [16]. In this, the Ti– Ge– N system is different from Ti– Si– N. The present paper focuses on the investigations of the nanostructure and local chemical composition of Ti– Ge– N polycrystalline films deposited by reactive magnetron sputtering. To answer how and where the atoms of the third element (Ge) are incorporated in the film seven complementary investigation techniques (Electron Probe Microanalyses (EPMA), Fourier Transform Infrared Spectroscopy (FTIR), Electron Energy-Loss Spectrometry (EELS), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Ellipsometry) were employed for film characterization. So we succeeded to show th
at the Ge atoms segregate to the TiN crystallite surface and limit the crystal growth by forming the TiGey amorphous phase
一个新的系统,钛锗-N ,已被选定为扩大知识三元多相氮化物薄膜。葛是在周期表像Si的第四组。然而,锗与氮的化学反应性比的Si和Ti [16]显著更低。在此,钛锗-N系统是由钛硅 - N。本论文侧重于纳米结构及磁控溅射钛锗-N多晶薄膜的局部化学成分的研究不同。要回答如何以及在何处的第三个元素( GE)的原子在影片中被合并7互补的调查技术(电子探针微量分析( EPMA ) ,傅立叶变换红外光谱(FTIR ) ,电子能量损失光谱( EELS) ,透射电子显微镜(TEM ) ,X射线光电子能谱(XPS ) ,X射线衍射(XRD) ,椭偏)被用于薄膜的表征。因此,我们成功地表明, Ge原子偏析到的TiN晶粒表面和通过形成TiGey非晶相限制了晶体生长
2. Experimental details
Ti– Ge– N thin films were deposited by DC reactive magnetron sputtering from confocal Ti and Ge targets in a gas mixture of N2+ Ar, at a total pressure of 0.9 Pa. The nitrogen partial pressure was 1.1%. The initial pressure in the reactor was lower than 3*10……5 Pa. The s
ubstrate holder was maintained in a fixed position parallel to the Ti target and rotated at 45 rpm during the deposition to obtain a uniform coating. The substrates were heated at 240-C. The diameter of the respective targets was 5 cm and the angle between targets was fixed at 54-. The germanium content in the films was varied by changing the applied power on the Ge target from 0 to 55 W, while maintaining the Ti target power at 120 W. GeNx and TiGey films were deposited in similar conditions to be used as reference in various investigations

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