测控技术与仪器类外文翻译、中英文翻译

1、过滤阴极真空电弧镀膜技术所制得氧化铝薄膜的结构和特性摘要：通过过滤阴极真空电弧镀膜技术制备氧化铝薄膜时，其内部结构、组成、形 态、光学和机械性能被详尽的描述，这些都与制备时氧气的流量有关。薄膜结构、组 成、形态和性能都是很重要的，随着氧气流量的增加，薄膜的结构也由非晶体经过 一系列变化到单品体，随着O/Zr原子比率的增加和Z离子由低氧化作用的状态转化 为Zr4+再一次形成非品体。形成这样的结构是由于其内部结构的变化而引起的，并 且影响其形态和机械性能，以致这种非品体薄膜表面有一些小簇，其光滑程度就像低 硬度的多晶体薄膜。当反射指数和系数相对接近最大值时，在发射率和光学带宽随着 O/Zr比增加时

2、，薄膜的组成来决其光学性能而非其密度。1.说明在大气压力下由于三种不同温度有多种不同靶形态结构，单晶体时低于1170OC， 四面体时为1170-2370oC，2370oC为立方体，知道2680oC时形成金属。Zr有很高的反 射指数，大光学带宽间距，和很低的光损失及在0.3-8范围内高透明度,所以被广泛的 应用于光学领域。此外，Zr具有很高的电介质，低泄露量等特点，最有可能代替做电解质的晶体管。 进而，由于Zr很低的传热性，它成为了装置中隔热层的首选。Z其他的特性如：高硬 度、高抗氧性也使其成为机械材料中的热门。至今为止，已经有很多制备Z的方法， 例如反应磁控溅射，离子辅助反应溅射，化学气相沉积

3、等。薄膜特性的优劣取决于制 备过程及其参数。过滤阴极真空电子弧镀膜技术，在低电压和高电流状态下工作。通过磁性机械过滤 器来防止微粒从阴极发射。它提供了一种具有很高能量的沉积离子源，远大于相应的 热蒸发和磁控溅射。能有效去处宏观无用微粒，很明显能提高薄膜质量并拓展其应用。 固有的高能量提高薄膜的附着性和密度。由于能力是离子辅助沉积中最重要的参数， 这种制备的方法已经有了一些应用，已经应用于在高热平衡和高SP3状态下碳薄膜的 制备，还合成了一些金属氧化物的薄膜。然而对我们最有利的是，很少有关过滤阴极 真空电子弧镀膜技术制备ZrO2薄膜的知识。我们现在的工作是系统研究在不同02流量与ZrO2薄膜的结

4、构、组成、表面形态和 性质之间的关系。我们的结论表明薄膜的结构、组成特性都与02流量有关系。 过滤阴极真空电子弧镀膜技术所制的薄膜特性与其他方法相比，更说明了该方法的优 越性。2.实验图1为制备设备。该图已经详细反应了这个系统，各个部分都表现了出来。该系 统有一个双倍滤光器，可以使弧自身发射出微粒。阴极Zr原子在120A电流下，阴、 阳极瞬间接触点燃喷出的浆体，该浆体是从一个400mT的磁场放射出来并压缩的。一 个旋转泵和一个冷凝泵可使这个系统的压力达到4X 10-6T。O2通过一个有很多小孔的铜 管进入Zr靶附近区域。这种发射O2的方式可使O2电离到最大程度，因此增加了与浆 体的接触使得Zr

5、与O2之间发生充分的反应。02流量可选择10-98sccm,在制备过程中， 随着O2流量的增加，靶的氧化更加充分。O2增加使得靶材充分氧化，并且损失了冷凝 粒子，使得制备的速率75nm/s降至35nm/s。在室温下薄膜生长在n-si和石英表面。 基片被放在制备室之中，按顺序被丙酮、酒精和未电离的水清洗。所制得的薄膜厚度 大约在200 nm。通过由CUK a做源的XRD法可得出薄膜所处阶段和晶体结构。光谱计记录下反射率 等参数，光学特性也被软件检测。主要特征和组成分析被XPS通过ALK辐射测得到。 不可使用没有清洗过的样品溅射，以免所溅射得到的薄膜化学组成发生变化。函岫 IVacuum are图

6、13.结果3.1结构图2表明在不同O2流量ZrO2薄膜由XRD测得的结构，在10sccm时，在曲线中对应着边缘处，而系统峰值在32.4oC附近，为标准的结构。这个高峰来自于没有完全氧 化的ZrO固体。由于类似现象可看出峰值点又是不对称的和急剧变化处。当02流量增 加至20sccm，一个最高峰是当晶体阶段，相对弱的高峰是多晶体阶段。氧气流量决定 峰值。我们可以检测出它是怎么影响薄膜结构的。在35sccm时，出现了更多的弱高峰， 在m(200)处峰值变得很弱，在m(-202m)变得很强。然而当氧气的流量增加至65sccm 时，薄膜由多品体变为无定形，在弯曲处出现更宽的高峰。结构的不同反应出02流量

7、 在薄膜结构形成中扮演了很重要的角色。正在一=aE 耳-L 国吝U A间1C seem=aE 耳-L 国吝U A间1C seem2C- sixm35 seen id) 50 seem (e) 65 sixeJ(W3D曲50702 Thetar IGLRE 1 XRD patterns forZr films deposited at different d?nite定流量范围内(20-50sccm)薄膜保持在多晶体状态，而在纯单晶体阶段在不同的 范围内。3.2化学组成和化学状态通过典型的XPS光谱测量可以得到由光电离子及Zr和0转变达到高峰，在与空气 接触后的抽样中经过观察C1S是主要表面组成

8、部分。在Zr3d和01S处出现两个高峰。 图4中可看到常态的元素和由XPS测得的局部光谱。频谱非常接近标准单品体的ZrO2。 两个高峰，Zr3d5/2和Zr3d3/2时的能量分别为181.8ev和184.2ev，非常接近在中标准 ZrO，并且是对称的，在氧化状态的薄膜中只有它。他们的强度比率和导致旋转轨道在 21.5ev和2.4ev的能量间隔和其他研究是一致的。一个不对称的高峰能分解为的 529.6evLBE能量和531ev的HBE，与报告中的那些类似。相比之下，薄膜沉积速率很低时，例如35sccm，Zr3d光谱是以某种方式不同的而O1S 频率是十分类似的。出现较低能量接近其边缘，有形式为Zr

9、,Zrn+,(n=1,2,3)氧化物存 在。可得出随着02流量的不同可转变为使得和发生充分的反应。氧化程度的不同也被 表明，薄膜中0和Zr的原子比率可由它们在峰值区域的灵敏度算出。01S的HBE是一 个小片段所以高峰不能被确定。正如预料，O/Zr比增加可导致更多氧化。可看到在薄 膜沉积速率为时，O/Zr比为1.98： 1接近原子比为2： 1，在65sccm及起以上，薄膜1_ 伽 , 面 14 _ilfia EFgg encjrgiy (W) b energy eV) c Binding energy (eV) FIGLftL 4 Zr3fl7 a. Jind OJf b. XPS local

10、spwtra of the film deposited at K) scc ni and Zr3rf c. at 35 seem3.3表面形态五表现了在65sccm时典型的薄膜。在薄膜表面，小簇由相同的冷凝的原子成。这表面相当干净和光滑，RMS粗燥率小于0.1nm在1umX1um区域内。上面提到的高能 量轰击微粒使得形成干净、光滑的表面，这些微粒运动时损失粒子，或者促进原子和 提供足够能量运动到生长表面相结合，再一次建议流量的边界值不影响原子的运动，与XRD测量结果一致。有趣的是，薄膜的形态似乎也被O2流动速率XRD分析出的薄膜结构的改变有关。在10sccm时，薄膜表面的簇会很大。这种簇的变

11、化可以反映出薄膜表面粗糙。XRD分 析出的薄膜结构的改变说明薄膜表面结构与。2的流量有关。换句话说，与无定型薄膜 相比较，这种多晶体薄膜在20-50sccm速率下在表面形成巨大的簇并且看起来很粗糙。02040BQ30hOxygen flow rate (socm)IKbURL 5 A top-viei- AFM image of the Him at 65 seem; b The RMS roughne of the IlJms at arying 3 flow mtes3.4机械性能薄膜的硬度是测量抵制塑性变形和确定载荷符合凹行区域的峰值。实际上，硬度通 过卸载数据所构成能量方程来表现。薄膜

12、的机械性能作为流量方程显示在图9,其值平 均至少出现了 3次，微硬度和是依赖于氧气流量。当流量由10sccm增加到20sccm，硬 度几乎维持为13.6GP，再增加流量会导致硬度急速提高。在35。50，硬度仍然在增加， 超出50sccm后，薄膜开始变软，并且在65sccm会降至13.4GPA。显然，硬度的改变非常接近在XRD式样中观察的。这表明硬度是由薄膜的结构确定而非特性确定其硬度，这与KAO的报告结果不一致。ia-280ia-280Oxygi&n flow rate (seem)FKUHE # The film hardness and Tccungs medulus at differe

13、nt O? flaw rates4.结论通过过滤阴极真空电弧镀膜技术制备薄膜，研究了在不同氧气流量时，薄膜的结 构、组成、形态、光学性能和机械性能，最终的流量达到了 98sccm。经研究发现O2 的流量是薄膜结构、组成、特性的重要参数。随着02流量的增加，薄膜的结构由无 定型到不同氧化率的单品体再到无定型；随着0/Zr原子比的增加，Zr原子由低氧化 率到Zr。这种与氧气流量有关的结构趋势会导致薄膜组成的改变并且决定表面形态 和薄膜的机械性能。g-q- yub.k. tayz.w. zhaoStructure and properties of zirconium oxide thin film

14、s prepared by filtered cathodic vacuum arcSchool of Electrical and Electronic Engineering, Nanyang Technological University,Singapore, 639798, SingapoReceived: 19 September 2003/Accepted: 17 January 2004Published online: 1 April 2004 Springer -Verlag 2004ABSTRACT Zirconium oxide (ZrO2) thin films de

15、posited atroom temperature by the filtered cathodic vacuum arc (FCVA) technique are detailed in terms of the film structure, composition, morphology, and optical and mechanical properties, which are tailored by the oxygen (O2) flow rate during deposition. The relationships between the film structure

16、, composition, morphology, and properties are emphasized. With an increasing flow rate, the film evolves in structure from amorphous, through a pure monoclinic phase with varying preferential orientation, to amorphous again, accompanied by an increase in the O /Zr atomic ratio and a conversion of Zr

17、 ions from low oxidation states into Zr4+. Such a structural trend arises from the change in composition, and influences the film morphology and mechanical properties so that the amorphous films exhibit small clusters on the surface and smoother morphology as well as lower hardness compared with the

18、 polycrystalline films. Thefilm composition rather than the density dominates the optical properties, where the transmittance and the optical band gap increase with increasing O/Zr values, while the refractive index and extinction coefficients behave conversely with the lowest refractive index (2.16

19、 at 550 nm) approaching the bulk value (2.2).PACS 68.55.Jk; 78.66.Nk; 68.37.Ps1. IntroductionZirconium oxide (ZrO2) has three temperature dependent polymorphic structures at atmospheric pressure. A monoclinic phase is stable at temperature below 11700 C, a tetragonalbetween 1170 and 2370 C, and a cu

20、bic from 2370 C to the melting point at 2680 C. ZrO2 is widely used in optical fields 1-3, because of its high refractive index,large optical band gap, and low optical loss and high transparency in the 0 .3-8 以 m range. In addition, ZrO2 is a promising candidate to replace silicon dioxide as the gat

21、e dielectric in transistors, due to its high dielectric constant (25), lowleakage current level, etc. 4-6. Furthermore, ZrO2 has potentialas a thermal barrier coating in devices due to its low thermal conductivity 7, 8. Other properties such as high hardness, large resistance against oxidation, also

22、 make it interesting as a mechanical material 9. To date, many efforts to prepare ZrO2 have been made by various deposition techniques, for example, reactive magnetron sputtering 10-13, ion-assisted reactive sputtering or evaporation deposition 8, 14-25, solgelmethods 26, chemical vapor deposition 4

23、, 17, and so on. The film properties are generally strongly dependent on the deposition process and parameters.The filtered cathodic vacuum arc technique (FCVA) 27-29, operated at low pressure, low voltage, and high current, effectively eliminates micro-sized (0.1-10 以 m) macroparticles from being e

24、mitting from cathode materials during arcing by means of mechanical, magnetic, or electrical filters,or a combination of these. It also provides an intense source of fully ionized deposition specieswith energies (50 150 eV) greater than counterparts produced in thermal evaporation or magnetron sputt

25、ering 30, 31. The removal of detrimental macro-particles undoubtedly improves the resulting film quality and extends the application of the deposition technique. The inherent high-energy could increase the film adhesion and the packing density. The full ionization of the deposition species allows ta

26、iloring of the film properties with substrate bias, since kinetic energy is one of the most important parameters as in ion beam assisted deposition (IBAD) 8. This technique has been demonstrated in the preparation of a diamond-like carbon film with high thermal stability and a high sp3 32, to fill t

27、renches 33, 34, as well as the synthesisof certain metal oxide films 35, 36. However, to the best of our knowledge, little work has been reported on ZrO2synthesis by the (FCVA) technique.In the present work, we systematically investigate the structural, chemical composition, optical, and mechanicalp

28、roperties of ZrO2 films deposited at different oxygen (O2) flow rates by FCVA. The emphasis is placed on the relationships between structure, composition, surface morphology, and properties of the films. Our results disclose that the structural and compositional properties of the films are considera

29、bly influenced by the O2 flow rate. The variation in compositioninduces structural transformation from amorphous through a pure monoclinic phase to amorphous again, and determines the optical properties,whereas the change in structure controls the mechanical properties and affects the surface morpho

30、logy. The properties of the films are also crosscomparedwith those of films prepared by other methods to highlight the FCVA features.2 ExperimentalA schematic diagram of the FCVA deposition system is shown in Fig. 1. The details regarding the main principles of the system have been described elsewhe

31、re 37. Briefly, the system incorporates an off-plane double bendfilter, which effectively removesmacro-particles originating from the arc itself. A Zr cathode (99 .98% pure) operated at 120 A dc current is ignited through instant contact between cathode and anode to obtain the plasma, which is steer

32、ed out by a toroidal magnetic field fixed at 40 mT to condense on a substrate. The base pressure of the system, evacuated by a rotary pump and a cryo-pump, can reach 4 X 10 6 Torr. O2 gas (99.99% pure) is led into the region near the Zr target through a copper tube on which many tiny holes are distr

33、ibuted.This way of introducing O2 is expected to maximize O2 ionization due to its relatively increased collision with the plasma, possibly promoting a chemical reaction between O2 and Zr. The O2 flow rate chosen here is varied from 10 to 98 sccm corresponding to 1 X 10 4 to 4.6 X 10 4 Torr. During

34、deposition, the deposition rate decreases from 75 to 35 nm/min with an increasing O2 flow rate as a result of increased .oxidization of the target, and collision-induced loss of condensing particles. The films are grown on n-Si (100) and quartz substrates at room temperature. All the substratesare s

35、equentially cleaned in acetone, alcohol, and de-ionizedwater prior to being loaded into the deposition chamber. All the films being investigated are generally around 200 nm thick. The film phase and crystal structure are identified by Xray diffraction (XRD) with a Cu Ka source at 1.54 A. Transmittan

36、ce and reflectance are recorded from 200 to 1100 nm with a spectrometer. Optical constants are obtained by fitting optical spectra with Scout software 38. Core level spectra and compositional analysis areGwiruwt Foe皿哩ccdff心亦FIGURE I A schema tic djagram of the FCVA depoydon systemand compositional a

37、nalysis are carried out by X-ray photoelectronspectroscopy (XPS) with monochromatic Al Ka radiation (I486.6 eV). No sputter cleaning of the samples is performed to avoid changes in chemical compositions induced by preferential sputtering. The spectrum obtained iscorrected by an adventitious C1 s pea

38、k at 284.6 eV. Surface morphology is measured by atomic force microscopy (AFM) in tapping mode (Dimension 3000 scanning probe microscope from Digital Instruments). The mechanical properties on a nano-scale are obtained by a nanoindentation techniqueapparatus (Hysitron Inc.) attached to the above AFM

39、 equipment.Nanoindentations were made using a Berkovich diamond indenter and the maximum loads applied were 500 p N. The indenter was loaded at 100 p N/s, held at peak load for 5 s and then finally unloaded at 100 p N/s.3 Results3.1 StructureFigure 2 shows theXRDpatterns for ZrO2 films deposited at

40、differentO2 flowrates.At 10 sccm, a broad but symmetric peak centered at around 324 is observed in curve (a), indicative of an amorphous structure. The peak is believed to come from an oxygen-deficient Zr-O solid solution 40.Wong et al, 13 also reported a similar phenomenon, where, however, the peak

41、 was unsymmetric and sharp. As the O2 flow rate increases to 20 sccm (Fig. 2b) ), one peak at 337。assigned to (200) planes of monoclinic phase (denoted as m(200) is predominant, accompanied by the appearance of other weak peaks also from the monoclinic phase. This rapid occurring of diffraction peak

42、s shows that so much oxygen is incorporated that sufficient ZrO2 crystallite forms which can be detected. The easy combination between Zr and O is possibly related to charged and therefore active emitted species, as well as further stimulated by energetic Zr particles bombarding the surface as in IB

43、AD. At ，一间 ，一间佩)10 sccnr (b；20 部W (c) 35 做m 母罢匠 l：d 50 sccrr VE E (g) 65 sccrr沁如5.C.607D2 rhetvFIGURE 2. XRD patterns for ZrO： films deposited at diiferent O2 flonv rate35 sccm, in addition to more weak peaks, them(200) peak becomes weaker while the m(-202) peak gets stronger. When the O2 flow rate

44、goes up to 50 sccm, the dominant peak is changed to m(-111) while many more monoclinic peaks are produced.3.2Chemical compositions and chemical statesIt was concluded from a typical XPS survey spectrum (not shown) that besides the peaks contributed by photoelectrons and Auger transitions of Zr and O

45、, Ck is observed as well, which is mainly from surface contamination after exposure of the sample to air. The two strong peaks at 185.9 and 533.2 eV are identified as Zr 3d and O1s, respectively. Fig. 4 presents the normalized Zr 3d (a) and O1s (b) XPS local spectra for the film prepared at 50 sccm.

46、 The spectra closely resemble those observed in standard monoclinic ZrO2 42. Two peaks, Zr 3d5/2 and Zr 3d3/2 observed at binding energies of 181.8 and 184.2 eV, very near to the values of Zr4+ in ZrO2 42, are symmetrical, denoting that only one oxidation state of Zr exists in the film. Their intens

47、ity ratio (I3d5/2/I3d3/2) and energy interval (A3d5/2 3d3/2) resulting from spin-orbit splitting are 1.5 and 2.4 eV, in agreement with other studies 20, 42. An asymmetric O1s peak can be decomposed into two components peaked at a low binding energy (LBE) of 529.6 eV and high binding energy (HBE) of

48、531.6 eV, quite comparable with reported ones 14, 43. It has been accepted that the LBE peak is assigned to the oxygenin zirconia 14, 20, 43 while the HBE is attributed to oxygen present in the hydroxide andbr adsorbed oxygen or carbonates or higher-valent oxides 14, 42, 44, 45.Matsuoka et al. 20 as

49、cribed it to oxygen possibly bound to Zr. In contrast, for the film deposited at the low flow rate, i.e., 35 sccm, the Zr 3d spectrum is somehow different whereas the O1s spectrum is very similar. A shoulder of the Zr 3d5/2 clearly appears at the lower binding energy side (Fig. 4c), indicating that

50、other oxidation states of Zr (Zrn+, n = 1, 2, 3) occur. This shoulder is attributed to Zr suboxides 14, 20. It can be concluded from this discrepancy that with increasing flow rate, Zrn+ (n W 3) will convert into Zr4+ due to a full reactionbetween Oand Zr in the films. This consistent variation in t

51、he oxidation state of Zr ions with the film composition was also reported in 20. The atomic ratio of Oto Zr (OZr) in the films can be calculated with their respective peak areas cali- brated by their sensitivity factors (0.66, 2.1, 0.66 for IBP 1B4 而555 甄184 ft B hiding cnigrgiy 爬町 b El ding energy

52、(eV) t Bindig energy (eV) FIGURL 4 Zr3d a. and OJj b XPS local spectra of rhe Him depaiited at 50 stem and Zv3d at 35 EccmO1s and Zr 3d). For the calculation, theO1s HBE peak is not included due to its small fraction. As expected, theO/Zr ratio increases with more addition of oxygen (not shown). Not

53、e that for the film deposited at 50 sccm, the O/Zr ratio obtained is approximately 1.98 : 1, near to the ideal stoichiometric ratio of 2 : 1. At 65 sccm and above, the films are over-stoichiometric (2.2 : 1).3.3Surface morphologyFigure 5a presents a typical top-view AFM image of the film at 65 sccm.

54、 On the film surface, the clusters composed of many condensing adatoms are uniformly distributed. The surface is quite clear and smooth, with its rootmean-square (RMS) roughness less than 01 nmover the area of 1 p mX 1 p m. This clearness and smoothness is associated with the above-mentioned high en

55、ergy of bombarding particles, which possibly removes loose particles (so-called “self-sputtering) or promotes bonding between adatoms and offers the adatoms enough lateral mobility on the growing surface 39, 46, again suggesting that the flow rate range selected does not greatly affect the adatoms m

56、obility, in accordance with the XRD results. Interestingly, the film morphology seems to be affected by the O2 flow rate as well. At 10 sccm, the clusters distributed on the film surface are similar in size to that for the film at 65 sccm. However, in the range of 20 to 50 sccm, larger clusters are

57、present on the surface. This change in cluster size is also reflected in the curve of roughness versus the O2 flow rate (Fig. 5b) the O2 flow rate (Fig. 5b), where the roughness is larger for a 20-50 sccm flow rate range. The flowrate-dependent surface morphology could be correlated with the film st

58、ructural change as drawn from XRD analysis. In other words,0204060&00204060&0bOxygen flow rate (sccmjFIGI-RE 5 a A top-view AFM image of the lilm at 65 seem; b The RMS roughness of the films it varying C2 flow ralescompared with the amorphous films, the polycrystalline films formed in a 20-50 sccm flowexhibit larger clusters on the surface and look relatively rougher.3.44echanical propertiesThe film hardness is a measure of resistance to plastic deformation and defined as the peak load divided by the corresponding indentation are