双频容性耦合等离子体相分辨发射光谱诊断

采用相分辨发射光谱法, 对双频容性耦合纯Ar和不同含O₂量的Ar-O₂混合气体放电等离子体的鞘层激发模式进行了探究. 在射频耦合电源上极板的鞘层区域处观察到两种电子激发模式: 鞘层扩张引起的电子碰撞激发模式和二次电子引起的电子碰撞激发模式; 并发现这两种激发模式均受到低频射频电源周期的调制. 在纯Ar放电等离子体中, 两种激发模式的激发轮廓相似; 而在Ar-O₂混合气放电等离子体中, 随着含O₂量的增加, 二次电子的激发轮廓变弱. 此外, 利用相分辨发射光谱法对不同含O₂量的Ar-O₂混合气放电下Ar的 750.4 nm谱线的平均低频电源周期轴向分布进行了研究, 得到了距耦合电源上极板约3.8 mm处为双频容性耦合射频等离子体的鞘层边界. 关键词： 双频容性耦合等离子体 等离子体鞘层 发射光谱     

短管螺旋波放电中等离子体参数测量和模式转化研究

对长度为45 cm的短放电管螺旋波放电等离子体进行了Langmuir探针、原子发射光谱以及集成电荷耦合检测器(ICCD)检测诊断,研究螺旋波等离子体的放电特性.Langmuir探针数据显示电子密度在射频功率增加过程中出现两次大幅增长,由此确认了放电模式的转换及螺旋波放电模式的出现.发射光谱测量结果与Langmuir探针测量的电子密度数据一致,发现Ar原子和Ar离子的谱线强度与放电模式变化有着密切相关性.而通过对不同放电模式的ICCD测量,获得射频功率吸收因放电模式转变而变化的方式,认为放电模式转换时电子行为和能量传递方式也发生着变化.     

Optical emission spectroscopy of Ar-N2 mixture plasma

Optical emission spectroscopy measurements are presented to characterize the different excitation and ionization processes of both atomic and molecular species in Ar-N₂ mixture plasma under different discharge conditions. Particularly, the emission intensities of nitrogen (0-0) band of second positive system at 337.1 nm and (0-0) band of first negative systems at 391.4 nm are used to determine the dependence of their radiative states on argon fraction in the mixture. It is observed that the addition of argon gas influences the radiative states differently due to their different populating mechanisms. The results demonstrate that the addition of argon to nitrogen plasma remarkably enhance the population of N₂(C³Π_u) radiative state through Penning excitation involving argon metastable states. The electron temperature is determined from Ar-I spectral line intensities, using Boltzmann's plot method and is found to depend on argon fraction in the mixture.     

Measurements of plasma parameters in capacitively coupled radio frequency plasma from discharge characteristics: Correlation with optical emission spectroscopy

Plasma parameters from the discharge characteristics of a 13.56 MHz capacitively coupled radio frequency Ar plasma are evaluated on the basis of homogeneous discharge model for wide range of operating pressure. The homogeneous discharge model of capacitively coupled radio frequency discharge is modified to take into account the nonlinear plasma series resonance effect. The effect of drift velocity of the electron due to change in radio frequency electric field and operating pressure is also considered. Considerable dependent of plasma parameters on the drift velocity of the electron as well as on the plasma series resonance effect are observed in low pressure. An irregular variation of calculated plasma density with operating pressure is observed, which is reconfirmed with optical emission spectroscopy.     

Collisional-radiative model for non-Maxwellian inductively coupled argon plasmas using detailed fine-structure relativistic distorted-wave cross sections

Our recently developed collisional-radiative model which included fine-structure cross sections calculated with a fully relativistic distorted-wave method [R.K. Gangwar, L. Sharma, R. Srivastava, A.D. Stauffer, J. Appl. Phys. 111, 053307 (2012)] has been extended to study non-Maxwellian inductively coupled argon plasmas. We have added more processes to our earlier collisional-radiative model by further incorporating relativistic distorted-wave electron impact cross sections from the 3p ⁵4sJ = 0, 2 metastable states, (1s ₃, 1s ₅ in Paschen’s notation) to the 3p ⁵5p (3p _i ) excited states. The population of various excited levels at different pressures in the range of 1–25 mTorr for an inductively coupled argon plasma have been calculated and compared with the recent optical absorption spectroscopy measurements as well as emission model results of Boffard et al. [Plasma Sources Sci. Technol. 19, 065001 (2010)]. We have also calculated the intensities of two emission lines, 420.1 nm (3p ₉ → 1s ₅) and 419.8 nm (3p ₅ → 1s ₄) and compared with measured intensities reported by Boffard et al. [J. Phys. D 45, 045201 (2012)]. Our results are in good agreement with the measurements.     

Diagnostics of an inductively coupled plasma in oxygen

Spatial time-integrated and space-time resolved profiles of excited atoms of oxygen were measured by optical emission spectroscopy for inductively coupled plasma (ICP) in oxygen. The discharge was sustained by a single turn coil supplied by 13.56 MHz RF generator delivering 100 and 200 W of power. The spatial emission profiles give the anatomy of the discharge required in order to understand the basic kinetics of ICP. Two types of nonuniformities are observed, azimuthal anisotropy and radial nonuniformity, both caused by spatially dependent energy supply to the electrons. Our experimental results show that oxygen is much more affected by azimuthal anisotropy and radial nonuniformity than argon. It is due to a different role of metastable atoms in kinetics of excitation, whereby stepwise excitation in oxygen is less probable than in argon. Optical emission data are supplemented by Langmuir probe measurements of electron densities and plasma potentials. Electrons gain energy from the time varying fields close to the coil, and the energy is not redistributed along the radius before it is dissipated in excitation, thus the observations are not consistent with the nonlocal theory predictions for the range of pressures, geometry, and power covered in this paper     

Measurements of argon metastable density using the tunable diode laser absorption spectroscopy in Ar and Ar/O_2

Densities of Ar metastable states 1s_5 and 1s_3 are measured by using the tunable diode laser absorption spectroscopy(TDLAS) in Ar and Ar/O2 mixture dual-frequency capacitively coupled plasma(DF-CCP). We investigate the effects of high-frequency(HF, 60 MHz) power, low-frequency(LF, 2 MHz) power, and working pressure on the density of Ar metastable states for three different gas components(0%, 5%, and 10% oxygen mixed in argon). The dependence of Ar metastable state density on the oxygen content is also studied at different working pressures. It is found that densities of Ar metastable states in discharges with different gas components exhibit different behaviors as HF power increases. With the increase of HF power, the metastable density increases rapidly at the initial stage, and then tends to be saturated at a higher HF power. With a small fraction(5% or 10%) of oxygen added in argon plasma, a similar change of the Ar metastable density with HF power can be observed, but the metastable density is saturated at a higher HF power than in the pure argon discharge. In the DF-CCP, the metastable density is found to be higher than in a single frequency discharge, and has weak dependence on LF power. As working pressure increases, the metastable state density first increases and then decreases,and the pressure value, at which the density maximum occurs, decreases with oxygen content increasing. Besides, adding a small fraction of oxygen into argon plasma will significantly dwindle the metastable state density as a result of quenching loss by oxygen molecules.     

Optical and spectroscopic properties of substituted oxa- and thiazole luminophores metalated with platinum metals

The cyclometalated [M(pbo)En]PF₆(M = Pd(II), Pt(II)), [M(pbo)₂En]PF₆ (M = Rh(III), Ir(III)), and [Rh(C∧N)₂En]PF₆ ((C∧N)^? are the deprotonated forms of 2-phenylbenzoxazole (pbo), 2,5-diphenyloxazole (dpo), 2-phenylbenzothiazole (pbt), 2-biphenyl-4-yl-5-phenyloxazole (bpo), and 2-biphenyl-4-yl-6-phenylbenzoxazole (bpbo) and En is ethylenediamine) complexes are studied by ¹H NMR spectroscopy, IR spectroscopy, and electronic absorption and emission spectroscopy. Metalation of luminophores leads to the formation of five-membered {M(C∧N)} cycles in the composition of plane-square and octahedral complexes of the cis-C,C structure. In addition to the intraligand (IL) π-π* optical transitions in the UV region, the complexes are characterized by long-wavelength metal-to-ligand charge-transfer (MLCT) absorption bands in the region of 366–416 nm. The phosphorescence of the complexes in the visible region (482–531 nm) is attributed to radiative transition from the mixed IL/MLCT electronically excited state. The temperature quenching of the phosphorescence of complexes is attributed to the thermally activated population of metal-centered electronically excited states with subsequent nonradiative deactivation.     

Time integral and time differential Mössbauer measurements on [57Co/Mn(bipy)3](PF6)2

The Mössbauer emission spectra of nucleogenic iron(II) complexes with a low spin (LS) ground state show two metastable iron(II) high spin (HS) states at low temperatures. In order to identify these metastable HS states, the compound [⁵⁷Co/Mn(bipyridine)₃](PF₆)₂ has been studied by time differential Mössbauer emission spectroscopy (TDMES) and optical lifetime measurements of excited electronic states in the corresponding Fe-doped Mn compound. The lifetime of one of the HS states of the nucleogenic iron(II) determined by TDMES has been measured to be the same as the lifetime of the laser-excited iron(II) electronic state.     

N2第二正带系发射光谱的理论计算及实验研究

本文利用分子光谱理论系统的计算和分析N₂第二正带系(C³∏_u→B³∏_g)的发射光谱, 以研究光谱强度的分布规律与不同温度条件和气体条件的关系. 基于N₂的三重态能级结构特性, 重点计算和讨论了发射光谱的概个重要参数: 通过求解高、低电子态的哈密顿矩阵得到了振转能级特性; 利用r质心近似法求取了能级间跃迁的电偶极矩函数和爱因斯坦跃迁概率; 进而计算了不同振动和转动温度条件下谱线的强度分布. 进行了N₂和Ar的混合放电实验, 利用实验光谱数据同理论结果进行拟合分析, 确定了N₂分子的振动温度和转动温度分别约为4300 K和800 K. 另外由于潘宁离化效应, N₂浓度减小时谱线强度呈现先增强后减弱的趋势. 实验结果很好的验证了N₂第二正带系光谱理论计算的正确性.     

脉冲射频容性耦合氩等离子体的发射探针诊断

利用工作在浮点模式下的发射探针,对500 Hz脉冲调制的27.12 MHz容性耦合氩气等离子体的空间电位和电子温度的时变特性进行了诊断.等离子体空间电位是通过测量强热状态下的发射探针电位获得的,而电子温度则是由发射探针在冷、热状态下的电位差来估算得到.测量结果表明:脉冲开启时,空间电位会快速上升并在300μs内趋于饱和;当脉冲关断后,空间电位经历了快速下降后趋于稳定的过程.电子温度在脉冲开启时存在过冲并趋于稳定的特征;而在脉冲关断期间,电子温度在300μs内则快速下降到0.45 e V后略有上升.无论在脉冲开启或关断期间,空间电位基本上都随功率和气压的变化存在有线性的依赖关系;而放电功率对脉冲开启期间过冲电子温度与稳态电子温度差异的影响较大.针对空间电位和电子温度在各阶段及不同放电条件下的时变特性,给出了相应的解释.     

13.56 MHz/2 MHz柱状感性耦合等离子体参数的对比研究

通过Langmuir双探针和发射光谱诊断方法,对比研究了驱动频率为13.56 MHz和2 MHz柱状感性耦合等离子体中电子密度和电子温度的径向分布规律.结果表明:在高频和低频放电中,输入功率的增加对等离子体参数产生了不同的影响,高频放电中主要提升了电子密度,低频放电中则主要提升了电子温度.固定气压为10 Pa,分别由高频和低频驱动时,电子密度的径向分布均为"凸型".而电子温度的分布差异比较明显,高频驱动时,电子温度在腔室中心较为平坦,在边缘略有上升;低频驱动时,电子温度随径向距离的增加而逐渐下降.为了进一步分析造成这种差异的原因,在相同放电条件下采集了氩等离子体的发射光谱图,利用分支比法计算了亚稳态粒子的数密度,发现电子温度的径向分布始终与亚稳态粒子的径向分布相反.继续升高气压到100 Pa,发现不论高频还是低频放电,电子密度的径向分布均从"凸型"转变为"马鞍形",较低气压时电子密度的均匀性有了一定的提升,但低频的均匀性更好.     

Effect of Excitation and Vibrational Temperature on the Dissociation of Nitrogen Molecules in Ar-N2 Mixture RF Discharge

Non-equilibrium argon-nitrogen mixture plasma generated at 13.56 MHz is characterized by optical emission spectroscopy and Langmuir probe techniques. The excitation and vibrational temperature are studied as a function of argon percentage in the mixture, at 30-Pa filling pressure and input RF powers of 200 and 300 watt, to find out their role in dissociation of N₂ molecules. In this work, the excitation temperature is determined from Ar-I emission line intensities by using the simple Boltzmann plot method and is found to increase with argon mixing in nitrogen plasma. In similar fashion, the vibrational temperature of second positive system has been determined and is found to also have increasing trend with argon addition. The effect of excitation and vibrational temperature on the nitrogen molecular dissociation level is also monitored. It is observed that N/N ₂ ratio increases with increase in excitation and vibrational temperature and falls slightly at the end.     

Optical properties of bicyclometalated Ir(III) and Rh(III) complexes of benzo[h]quinoline with (N∧S)− and (N∧O)− chelating ligands

[M(bzq)₂(N∧X)] complexes (M = Rh(III), Ir(III); (bzq)^? is the deprotonated form of benzo[h]quinoline, and (N∧X)^? are 2-thiolpyridine, 2-hydroxypyridine, and 2-thiolbenzothiazole ions) are studied by absorption and emission spectroscopy and voltammetry. The long-wavelength absorption bands of [Rh(bzq)₂(N∧X)] in the range of 420–424 nm are attributed to the optical metal-to-ligand charge transfer (MLCT) transitions, while the low-temperature (77 K) phosphorescence in the range of 490–610 nm is assigned to the intraligand (IL) transition of the {Rh(bzq)₂} metal-complex fragment. The phosphorescence of the [Ir(bzq)₂(N∧X)] complexes in liquid solutions in the range of 585–675 nm is assigned to the radiative MLCT transition, while the low-temperature (77 K) phosphorescence occurs from the thermally nonequilibrium MLCT and IL excited states of the {Ir(bzq)₂} metal-complex fragment.     

悬浮型微波共振探针在电负性容性耦合等离子体中电子密度的测量

本文首先利用悬浮型微波共振探针测量了Ar等离子体的电子密度,并与朗缪尔双探针的测量结果进行了比较,表明了微波共振探针在低密度等离子体测量的可行性.对40.68 MHz单射频容性耦合Ar/SF₆和SF₆/O₂等离子体的测量结果表明:电负性气体SF₆掺入Ar等离子体显著降低了等离子体电子密度,但随着增加SF₆的流量,电子密度表现为缓慢下降;而O₂掺入SF₆等离子体中,电子密度则随着O₂流量的增加表现为持续的下降.另外,40.68 MHz/13.56 MHz双频激发的SF₆/O₂容性耦合离子体的电子密度并不随低频功率的变化而变化.本文对上述的实验现象进行了初步的解释.     

Wavelength-modulation spectroscopy using a frequency-doubled current-modulated diode laser

We have studied atomic absorption in an argon discharge by wavelength-modulation spectroscopy with a frequency-doubled diode laser. The tunable wavelength-modulated radiation at 430 nm was generated by frequency doubling a current-modulated 860-nm diode laser in a KNbO₃ crystal. 2f-, 4f- and 6f-harmonic spectra as a function of diode laser modulation depth were measured on a Doppler-broadened sample of excited argon atoms produced in a capacitively coupled plasma chamber. Characterisation of the harmonic signals was accomplished. Minimum detectable absorbances of 7.7×10^-5 and 1.9×10^-4 based on a 3σ criterion (σ being the standard deviation of the noise) were estimated for 2f- and 4f-harmonic detection of the frequency-doubled radiation with a time constant of 0.1 s. The concentrations of argon in the 1s₄ state were found to be in the range of 3×10⁸ to 1.2×10¹¹ cm^-3 for the experimental conditions studied. Received: 25 February 2002 / Revised version: 4 April 2002 / Published online: 14 May 2002     

Optical properties of p-type CuAlO2 thin film grown by rf magnetron sputtering

We report the structural and optical properties of copper aluminium oxide (CuAlO₂) thin films, which were prepared on c-plane sapphire substrates by the radio frequency magnetron sputtering method. X-ray photoelectron spectroscopy (XPS) along with X-ray diffraction (XRD) analysis confirms that the films consist of delafossite CuAlO₂ phase only. The optical absorption studies show the indirect and direct bandgap is 1.8 eV and 3.45 eV, respectively. Room temperature photoluminescence (PL) measurements show three emission peaks at 360 nm (3.45 eV), 470 nm (2.63 eV) and 590 nm (2.1 eV). The first one is near band edge emission while the other two are originated from defects.     

Evolution of vacuum ultraviolet emission in dual-frequency capacitively coupled plasmas

In plasma material processing, vacuum ultraviolet (VUV) emission is released from gas discharges, leading to undesirable results. Energetic VUV photons enable the creation of an electron-hole pair current when their energy is larger than the bandgap energy of the plasma-facing top layer during plasma material processing. For example, the high energy of VUV photons from helium (21.2 eV), argon (11.6 eV), and oxygen (13.6 eV) is sufficient to generate induced currents in SiO₂ thin films. These feedstock gases are widely used in many procedures utilizing low-temperature industrial plasmas. Thus, the VUV emission evolution with both the power ratio between high (60 MHz) and low (2 MHz) frequencies and pulse duty ratio of the low-frequency radio frequency (rf) power in a dual-frequency capacitively coupled plasma, which is indispensable in modern plasma etching processes, was investigated. Both the power ratio between high and low frequencies and the pulse duty ratio changed the electron temperature, leading to evolution of the VUV emission intensity.     

Optogalvanic spectroscopy of metastable states in Yb+

The metastable ²F_7/2 and ²D_3/2 states of Yb⁺ are of interest for applications in metrology and quantum information and also act as dark states in laser cooling. These metastable states are commonly repumped to the ground state via the 638.6 nm ²F_7/2–¹D[5/2]_5/2 and 935.2?nm ²D_3/2–³D[3/2]_1/2 transitions. We have performed optogalvanic spectroscopy of these transitions in Yb⁺ ions generated in a discharge. We measure the pressure broadening coefficient for the 638.6 nm transition to be 70±10?MHz?mbar^?1. We place an upper bound of 375 MHz/nucleon on the 638.6 nm isotope splitting and show that our observations are consistent with theory for the hyperfine splitting. Our measurements of the 935.2 nm transition extend those made by Sugiyama et al., showing well-resolved isotope and hyperfine splitting (Sugiyama and Yoda in IEEE Trans. Instrum. Meas. 44: 140, 1995). We obtain high signal-to-noise, sufficient for laser stabilisation applications (Streed et al. in Appl. Phys. Lett. 93: 071103, 2008).     

Collisionless bounce resonance heating in dual-frequency capacitively coupled plasmas

We present the experimental evidence of the collisionless electron bounce resonance heating (BRH) in low-pressure dual-frequency capacitively coupled plasmas. In capacitively coupled plasmas at low pressures when the discharge frequency and gap satisfy a certain resonant condition, the high energy beamlike electrons can be generated by fast sheath expansion, and heated by the two sheaths coherently, thus the BRH occurs. By using a combined measurement of a floating double probe and optical emission spectroscopy, we demonstrate the effect of BRH on plasma properties, such as plasma density and light emission, especially in dual-frequency discharges.