Effects of outgassing on the reactive sputtering of piezoelectric AlN thin films

A series of study of the effects of outgassing on pulsed-DC reactive sputtering of highly (0002)-textured AlN thin film was conducted with systematically adjusted sputtering parameters like working pressure, atmosphere, and temperature. The film quality was evaluated by its rocking curve width and residual stress, both utilizing X-ray diffraction methods, as well as by SEM and XPS analyses. It is found that with lower outgassing all the above-mentioned sputtering parameters become less effective on both rocking curve width and residual stress. The rocking curve FWHM (Full Width at Half Maximum) measurements even exhibit apparently insensitive regions to the sputtering parameters, and accompanied threshold behaviors as well. XPS analysis reveals higher oxygen content while SEM observation shows thinner and slanter columnar structure in the AlN film when outgassing is higher upon sputtering.     

Effects of pulse parameters on the pulsed-DC reactive sputtering of AlN thin films

A series of studies on the pulsed-DC reactive sputtering of highly (002)-textured aluminum nitride (AlN) thin films was conducted with systematically adjusted pulse parameters including reverse voltage, pulse frequency, and pulse duration. The film quality was evaluated by the full width at half maximum (FWHM) of the (002) rocking curve as well as the (002) peak intensity. In the asymmetric bipolar mode, the FWHM increases while the peak intensity decreases with reverse voltage, implying a detrimental effect of reverse voltage on the quality of AlN film. Whereas in the unipolar mode, the film quality improves with pulse frequency as evidenced by the decreasing FWHM and increasing peak intensity. It is also found that there is a critical pulse duration of about 500 μs, beyond which the FWHM starts to increase while the peak intensity starts to decrease due to target poisoning. Typical measurements on thus-optimized AlN film show a roughness of 1.7 nm and a (002) FWHM of less than 1.9°.     

射频反应溅射中N2分量对TiN薄膜性质的影响

用射频反应溅射的方法制备了TiN薄膜，其晶体结构与电阻率都与溅射气氛中N2分量有直接关系。随着N2分量由5％增加到50％，薄膜先是呈现（111）的择优取向，后是呈现（200）的取向，最后没有衍射峰出现，结构趋于无定型，于此同时，电阻率也由接近金属的良好导电性变为半导体的导电性。     

反应射频磁控溅射制备高k氧化锆薄膜及介电性能的研究

在氧气和氩气的混合气体中,在O2/Ar混和气总流量固定的条件下,通过调节O2/Ar流量比,采用反应RF磁控溅射法制备了具有高介电常数的氧化锆薄膜。通过透射电子显微镜(TEM)和原子力显微镜(AFM)研究了O2/Ar流量比与薄膜微观组织和结构、表面平整度之间的关系,并测试分析了在不同O2/Ar流量比下溅射沉积的Al/ZrO2/SiO2/n型Si叠层结构的C V特性曲线。实验结果表明O2/Ar流量比与薄膜微观组织和结构有一定的关系。纯氧气氛下沉积的ZrO2薄膜基本上为纳米级的微晶,晶体结构为单斜结构(a=5.17、b=5.26、c=5.3、α=γ=90°,β=80.17°),在O2/Ar流量比为1∶4混合气氛下制备出了具有非晶结构的均质ZrO2薄膜;低的O2/Ar流量比下溅射得到的ZrO2薄膜样片,均方根粗糙度较低,表面平整度较好;在O2/Ar流量比为1∶4左右时,ZrO2薄膜的相对介电常数达到25。     

中频磁控反应溅射AlN薄膜及微观结构研究

采用中频磁控反应溅射工艺进行了氮化铝薄膜的制备,对沉积速率、晶体结构和表面形貌与氮气流量和溅射功率之间的变化关系进行了研究。结果表明,通过调节N2流量和溅射功率选择性地获得非晶态和沿着c轴方向择优生长的晶态AlN薄膜。在化合物沉积模式下,增加溅射功率和增加反应气体流量均有利于获得非晶态AlN薄膜,并且减小薄膜表面粗糙度,获得光滑的AlN薄膜,并采用薄膜生长原理对这种现象进行了解释。     

Deposition of c-axis orientation aluminum nitride films on flexible polymer substrates by reactive direct-current magnetron sputtering

Aluminum nitride (AlN) piezoelectric thin films with c-axis crystal orientation on polymer substrates can potentially be used for development of flexible electronics and lab-on-chip systems. In this study, we investigated the effects of deposition parameters on the crystal structure of AlN thin films on polymer substrates deposited by reactive direct-current magnetron sputtering. The results show that low sputtering pressure as well as optimized N₂/Ar flow ratio and sputtering power is beneficial for AlN (002) orientation and can produce a highly (002) oriented columnar structure on polymer substrates. High sputtering power and low N₂/Ar flow ratio increase the deposition rate. In addition, the thickness of Al underlayer also has a strong influence on the film crystallography. The optimal deposition parameters in our experiments are: deposition pressure 0.38 Pa, N₂/Ar flow ratio 2:3, sputtering power 414 W, and thickness of Al underlayer less than 100 nm.     

Characterization of zirconium oxynitride films obtained by radio frequency magnetron reactive sputtering

Thin ZrN_xO_y films are deposited on Si (100) substrates by radio frequency (RF) reactive magnetron sputtering of a zirconium target in an argon-oxygen-nitrogen mixture. The Φ_N2/Φ_{(Ar + N2 + O2)} ratio was varied in the range 2.5%-100% while the oxygen flux was kept constant. The films were characterized by combining several techniques: X-ray photoelectron spectroscopy, X-ray diffraction and Secondary Ion Mass Spectroscopy. The relationship between structural and compositional properties and the sputtering parameters was investigated. Increasing nitrogen partial pressure in the gas mixture, a chemical and structural evolution happens. At lowest nitrogen flux, ZrN cubic phase is formed with a very small amount of amorphous zirconium oxynitride. At highest nitrogen flux, only crystalline ZrON phases were found. For the films obtained between these two extremes, a co-presence of ZrN and ZrON can be detected. In particular, chemical analysis revealed the co-presence of ZrO₂, ZrN, ZrON and N-rich zirconium nitride which is correlated with the Φ_N2/Φ_{(Ar + N2 + O2)} values. A zirconium nitride crystal structure with metal vacancies model has been considered in order to explain the different chemical environment detected by X-ray photoelectron spectroscopy measurements. The metal vacancies are a consequence of the deposition rate decreasing due to the target poisoning. It's evident that the growth process is strongly influenced by the zirconium atoms flux. This parameter can explain the structural evolution.     

Electrical properties of AlNxOy thin films prepared by reactive magnetron sputtering

Direct current magnetron sputtering was used to produce AlN_xO_y thin films, using an aluminum target, argon and a mixture of N₂ + O₂ (17:3) as reactive gases. The partial pressure of the reactive gas mixture was increased, maintaining the discharge current constant. Within the two identified regimes of the target (metallic and compound), four different tendencies for the deposition rate were found and a morphological evolution from columnar towards cauliflower-type, ending up as dense and featureless-type films. The structure was found to be Al-type (face centered cubic) and the structural characterization carried out by X-ray diffraction and transmission electron microscopy suggested the formation of an aluminum-based polycrystalline phase dispersed in an amorphous aluminum oxide/nitride (or oxynitride) matrix. This type of structure, composition, morphology and grain size, were found to be strongly correlated with the electrical response of the films, which showed a gradual transition between metallic-like responses towards semiconducting and even insulating-type behaviors. A group of films with high aluminum content revealed a sharp decrease of the temperature coefficient of resistance (TCR) as the concentration ratio of non-metallic/aluminum atomic ratio increased. Another group of samples, where the non-metallic content became more important, revealed a smooth transition between positive and negative values of TCR. In order to test whether the oxynitride films have a unique behavior or simply a transition between the typical responses of aluminum and of those of the correspondent nitride and oxide, the electrical properties of the ternary oxynitride system were compared with AlN_x and AlO_y systems, prepared in similar conditions.     

反应磁控溅射制备c轴择优取向氮化铝薄膜的研究进展

AlN薄膜在力学、光学和电子学中有着广泛的应用,而反应磁控溅射技术由于沉积温度低,成本低,非常适合沉积应用于GHz通信系统中体声波(BAW)和表面声波(SAW)器件的(002)取向的AlN薄膜.本文先概述了反应溅射的两个模型,然后综述了工艺参数包括溅射气压、溅射功率、氮气浓度、衬底温度、衬底种类、靶基距、薄膜厚度、衬底偏压、退火处理等对AlN薄膜生长和性能的影响.     

Preparation of highly oriented AlN thin films on glass substrates by helicon plasma sputtering and design of experiments

Aluminum nitride (AlN) thin films were deposited by a helicon plasma sputtering system with a radical cell. We investigated the effects of eight sputtering control factors on the crystal orientation of the films by design of experiments and the analysis of variance (ANOVA) in order to prepare highly oriented AlN thin films on silica glass substrates. Consequently, it was proved statistically that the distance between a target and a substrate, the sputtering pressure and the substrate temperature are significant control factors for the crystal orientation of the films. Especially, the distance is the most important factor of the eight control factors, which has not been reported so far. On the other hand, the effects of the cathode r.f. coil power, the radical cell power, the nitrogen concentration, the sputtering time and the cathode power are not statistically significant. Moreover, a detailed investigation of the dependence of the orientation on the three important control factors was carried out to optimize the sputtering conditions. The full width at half-maximum (FWHM) of the X-ray rocking curve of the film deposited under the optimized sputtering conditions is 2.4° (σ=1.3°). This orientation is the highest in the AlN thin films deposited on amorphous substrates reported to our knowledge.     

反应溅射Ti-Al-Si-N纳米晶复合薄膜的微结构与力学性能

采用Ar、N2和SiH4混合气体反应溅射制备了一系列不同Si含量的Ti-Al-Si-N薄膜，并采用EDS、AES、XRD、TEM和微力学探针研究了薄膜的微结构和力学性能。结果表明通过控制混合气体中SiH4分压可以方便地获得不同Si含量的Ti-Al-Si-N纳米晶复合薄膜。当Si含量达到3．5％(原子分数)时，薄膜中出现TiSix界面相，造成(Ti，Al)N晶粒细化，使薄膜力学性能得到提高，硬度和弹性模量的最高值分别为36．0GPa和400GPa。进一步提高Si含量，薄膜的力学性能逐渐降低。     

Influence of incidence angle and distance on the structure of aluminium nitride films prepared by reactive magnetron sputtering

Aluminum nitride (AlN) films were reactively deposited on (100) oriented silicon substrates by reactive radio frequency (RF) magnetron sputtering for different incidence angles and distances between substrate and target.X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to consider the influence of process parameters such as reactive gas flow rate, grazing incidence angle (α), and distance (d) between substrate and target surface on the property of AlN films. XRD results showed that AlN film prepared at a constant distance (d) of 3 cm and an incidence angle of 45° revealed a mixture of AlN (002), (100), and (101) planes, while the film prepared at α = 0° revealed a strong AlN (002) orientation which has a perpendicular growth direction to the substrate surface. AFM results showed that AlN film prepared at α = 0° exhibited more flat surface morphology than that of film prepared at α = 45°.     

氧分压对RF磁控溅射ZrO2薄膜生长特性的影响

采用反应射频(RF)磁控溅射法在n型(100)单晶S基片上沉积了ZrO2膜,研究了氧分压与ZrO：薄膜的表面粗糙度和沉积速率、SiO2中间界层的厚度以及ZrO2薄膜的折射率之间关系。结果表明：随着氧分压增高,薄膜的沉积速率降低,表面粗糙度线性地增加;在低的氧分压情况下,Si基片表面的本征SiO2层的厚度增加幅度较小,在高的氧分压情况下,Si基片表面的本征SiO2层的厚度有较大幅度地增加;在O2／Ar混和气氛下,溅射沉积的ZrO2薄膜的折射率受氧分压的影响不显著,而在纯氧气气氛环境下,ZrO2薄膜的折射率明显偏低,薄膜的致密性变差。     

Synthesis of AlN by reactive sputtering

We present a systematic study of the sub-band gap optical absorption coefficients (hν) in the range 1.2–6 eV vs. deposition-temperature (T_s from 27 to 450°C) films deposited on silica by 13.6 MHz magnetron sputtering of an Al target with 53 and 72% N₂ in the reactive mixture. X-ray diffraction, infrared absorption and Raman diffusion are also presented, mainly on films deposited on Si in the same run to help in the characterisation of the films. All signals are specific of AlN polycrystalline films, which are of better quality when deposited with 72% N₂. The lowest sub-band gap optical absorption around 5×10² cm⁻¹ is obtained for deposition on silica at T_s=300°C with 72% N₂ and is close to that of heteroepitaxial films deposited on sapphire.     

反应RF磁控溅射法制备非晶氧化硅薄膜及其特性研究

在氧气和氩气的混合气体中,在没有额外加热的条件下用反应射（RF）溅射硅靶制备了非晶氧化硅（a-SiO2)薄膜,并测试分析了薄膜的结构和电特性与O2／Ar流量比的关系。当固定氩气流量,改变氧气流量时,薄膜沉积速率先急剧减少,再增大,然后又减少。当O2／Ar≥0．075时,得到满足化学配比的氧化硅薄膜。并且,随着O2／Ar流量比的增大,薄膜的电阻,电场击穿强度都有所增大,而在HF缓冲溶液（BHF）中的腐蚀速率下降,所有的样品中无明显的H－OH水分子的红外吸收峰。比较发现反应射频（RF）磁控溅射法制备的a-SiO2薄膜具有良好的致密性和绝缘性。     

非平衡磁控溅射沉积Ta-N薄膜的结构与电学性能研究

采用直流反应非平衡磁控溅射技术在单晶Si(100)和玻璃表面沉积氮化钽(Ta-N)薄膜,分别测试了薄膜的结构、成分、电阻率和吸收光谱,研究了氮氩流量比(N2∶Ar)变化对Ta-N薄膜的结构和电学性能的影响.研究结果表明随N2∶Ar增加,依次生成六方结构的γ-Ta2N、面心立方结构(fcc)的δ-TaNx、体心四方结构(bct)的TaNx;N2∶Ar在0.2～0.8的范围内,Ta-N薄膜中只存在着fcc δ-TaNx;当N2∶Ar＞1之后,Ta-N薄膜中fcc δ-TaNx和bct TaNx共存.Ta-N薄膜电阻率随N2∶Ar流量比增加持续增加,当N2∶Ar为1.2时,薄膜变为绝缘体,光学禁带宽度为1.51eV.     

Deposition by magnetron sputtering and characterization of indium tin oxide thin films

In this work the properties of indium tin oxide (ITO) films deposed on glass substrates by magnetron sputtering technique in the temperature range below 200 °C are studied by various methods. The physical properties of ITO thin films have been investigated using optical transmittance, photoluminescence, atomic force microscopy, ellipsometry, Hall-effect and four point probe methods. It is established that properties of ITO layers depend drastically on the temperature and oxygen partial pressure during the deposition process and exhibit some peculiarities of the surface morphology. It is found that the band gap energy of this material varies in the energy range from 4.1 to 4.4 eV and depends on the growth conditions. It is suggested that local deviations from the stoichiometry and defects are the main physical reasons of Burstein-Moss shift of the optical band gap.     

Epitaxial growth of AlN on single crystal Mo substrates

We have grown AlN films on single-crystalline Mo(110), (100), and (111) substrates using a low temperature pulsed laser deposition (PLD) growth technique and investigated their structural properties. Although c-axis oriented AlN films grow on Mo(100), the films contain 30° rotated domains due to the difference in the rotational symmetry between AlN(0001) and Mo(100). AlN films with only poor crystalline quality grow on Mo(111) substrates, probably due to the poor surface morphology and high reactivity of the substrates. On the other hand, single crystal AlN films grow epitaxially on Mo(110) substrates with an in-plane relationship of AlN[11-20] // Mo[001]. Reflection high-energy electron diffraction or electron backscattered diffraction analysis has revealed that neither in-plane 30° rotated domains nor cubic phase domains exist in the AlN films. X-ray reflectivity measurements have revealed that the heterointerface between AlN and Mo prepared by PLD at 450 °C is quite abrupt. These results indicate that PLD epitaxial growth of AlN on single crystal Mo substrates is quite promising for the fabrication of future high frequency filter devices.     

衬底温度对磁控溅射法制备ZnO薄膜结构及光学特性的影响

采用射频反应磁控溅射法在玻璃衬底上制备了具有c轴高择优取向的ZnO薄膜,利用X射线衍射仪、扫描探针显微镜及紫外分光光度计研究了生长温度对ZnO薄膜的结构及光学吸收和透射特性的影响.结果表明,合适的衬底温度有利于提高ZnO薄膜的结晶质量;薄膜在紫外区显示出较强的光吸收,在可见光区的平均透过率达到90%以上,且随着衬底温度的升高,薄膜的光学带隙减小、吸收边红移.采用量子限域模型对薄膜的光学带隙作了相应的理论计算,计算结果与实验值符合得较好.     

直流反应溅射TiO2薄膜的制备及其性能研究

采用直流反应磁控溅射的方法,溅射高纯钛靶在ITO石英衬底上制备了TiO2薄膜.用XRD、Raman光谱、AFM和紫外-可见光分光光度计分别测试了TiO2薄膜的结构、表面形貌和紫外-可见光透射谱,研究了工艺因素中溅射气压、氧氩比和退火温度对薄膜结构的影响.采用C(胶)/TiO2/ITO三层结构研究了锐钛矿TiO2薄膜的紫外光响应.实验结果表明较低的溅射气压、合适的氧氩比和较高的退火温度有利于锐钛矿TiO2薄膜的结晶.在2 V的偏压下,锐钛矿TiO2薄膜的紫外光响应上升迟豫时间约为3 s,稳定光电流可达到2.1 mA,对紫外光的灵敏性和稳定的光响应表明TiO2薄膜有可能成为一种新的紫外光探测器材料.