CHF3 Dual-Frequency Capacitively Coupled Plasma by Optical Emission Spectroscopy

We investigate the intermediate gas phase in the CHFs 13.56 MHz/2 MHz dual-frequency capacitively couple plasma （CCP） for the SiCOH low dielectric constant （low-k） film etching, and the effect of 2MHz power on radicals concentration. The major dissociation reactions of CHF3 in 13.56MHz CCP are the low dissociation bond energy reactions, which lead to the low F and high CF2 concentrations. The addition of 2MHz power can raise the probability of high dissociation bond energy reactions and lead to the increase of F concentration while keeping the CF2 concentration almost a constant, which is of advantage to the SiCOH low-k films etching. The radical spatial uniformity is dependent on the power coupling of two sources. The increase of 2 MHz power leads to a poor uniformity, however, the uniformity can be improved by increasing 13.56 MHz power.     

The effect of pretreatment on adhesive strength of Cu-plated liquid crystal polymer (LCP)

Copper metallization on LCP was carried out by means of electroless plating followed by electroplating and the effect of pretreatment on the adhesive strength of the Cu-plated LCP was investigated in detail. Compared with the other etching agents used here, potassium permanganate was found to be the most effective and the optimum etching time is 20 min. With potassium permanganate as the etching agent, the adhesive strength could reach 12.08 MPa, which is much higher than the reported maximum adhesive strength (lower than 8.0 MPa). XPS spectra of LCP film indicated that hydrophilic groups were introduced into the LCP surface by etching, creating a nanometer-scale surface roughness and improving the wettability between copper and LCP. SEM and AFM observations revealed that the distinctly increased adhesive strength could be attributed to the improved wetting and the mechanical interlocking effect. The failure mode of Cu-plated LCP film was found to be dependent on the etching time. When the etching time was short, the failure mode of Cu-plated LCP film was mainly adhesive. As the etching time increased, cohesive failure gradually occurred, causing an adhesive/cohesive mixed failure mode.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

Basic mechanisms in laser etching and deposition

Laser-induced chemical processing of solid surfaces has the potential for being an important and powerful technique for fabrication of a variety of devices. Successful applications rest on a detailed understanding of the nature of laser-induced reactions and their effects on the properties of materials. In this paper fundamental studies illustrating key features of laser etching and deposition are reviewed. Topics covered include the effect of the choice of precursor and deposition conditions on film composition and morphology, self-propagation of exothermic reactions, thermal and electronic effects in laser-assisted etching of semiconductors, metals and polymers, and special aspects of laser-surface photophysics as they may affect chemical reactions.     

同步辐射光激励的二氧化硅薄膜刻蚀研究

利用热氧化法在硅晶片上生长SiO₂薄膜，结合光刻和磁控溅射技术在SiO₂薄膜表面制备接触型钴掩模，通过掩模方法在硅表面开展了同步辐射光激励的表面刻蚀研究，在室温下制备了SiO₂薄膜的刻蚀图样.实验结果表明：在同步辐射光照射下，通入SF₆气体可以有效地对SiO₂薄膜进行各向异性刻蚀，并在一定的气压范围内，刻蚀率随SF₆气体浓度的增加而增加，随样品温度的下降而升高；如果在同步辐射光照射下，用SF₆和O₂的混合气体作为反应气体，刻蚀过程将停止在SiO₂/Si界面，即不对硅刻蚀，实现了同步辐射对硅和二氧化硅两种材料的选择性刻蚀；另外，钴表现出强的抗刻蚀能力，是一种理想的同步辐射光掩模材料. 关键词： 同步辐射刻蚀 接触型钴掩模 二氧化硅薄膜     

Selective etching characteristics of the AgInSbTe phase-change film in laser thermal lithography

In the current work, the etching selectivity of the AgInSbTe phase-change film in laser thermal lithography is reported for the first time. Film phase change induced by laser irradiation and etching selectivity to crystalline and amorphous states in different etchants, including hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, sodium hydroxide, sodium sulfide, ammonium sulfide and ammonium hydroxide, are investigated. The results indicated that ammonium sulfide solvent (2.5 mol/L) had excellent etching selectivity to crystalline and amorphous states of the AgInSbTe film, and the etching characteristics were strongly influenced by the laser power density and laser irradiation time. The etching rate of the crystalline state of the AgInSbTe film was 40.4 nm/min, 20 times higher than that of the amorphous state under optimized irradiation conditions (power density: 6.63 mW/μm² and irradiation time: 330 ns), with ammonium sulfide solvent (2.5 mol/L) as etchant. The step profile produced in the selective etching was clear, and smooth surfaces remained both on the step-up and step-down with a roughness of less than 4 nm (10×10 μm). The excellent performance of the AgInSbTe phase-change film in selective etching is significant for fabrication of nanostructures with super-resolution in laser thermal lithography.     

Polymer photoablation under windowless VUV hydrogen or helium discharge lamp

In this work, the photoablation of PolyPhenyl-Quinoxaline (PPQ) films is investigated by using the vacuum ultraviolet (VUV) incoherent emission (λ<160nm) from a novel windowless hydrogen (or helium) discharge lamp. A tentative explanation of the film etching process is given through the photochemical reactions which take place in the polymer under VUV illumination.     

Bistability and explosive transients in surface reactions: the role of fluctuations and spatial correlations

We study the dynamics of a class of catalytic surface reactions in which an adsorbed molecule undergoes dissociation giving oxygen, which then rapidly reacts with H adatoms to give water. The reaction-diffusion equations predict bistability and explosive transients similar to those observed in several low-pressure experiments. Kinetic Monte Carlo simulations reveal however that the dynamics can be strongly affected by spontaneous, inhomogeneous fluctuations of composition on the surface. In particular, bifurcation points can be displaced and the explosive character of the transients can be lost, depending on a subtle balance between the rate of reaction and the mobility of the decomposing species. These effects can be quantified on the basis of a stochastic formulation of the dynamics taking into account spatial correlations. This approach allows to better delimit the applicability of the traditional reaction-diffusion modelling in the case of reactions such as the reduction of NO _x or SO _x species on catalytic surfaces.     

Electron and ion beam induced heating effects in solids measured by laser interferometry

A sensitive interferometric technique has been applied for studying the thermal displacement of thin film heated by electron or ion beams. The steady state displacement has been measured and we discuss the dependence on material properties and film thickness showing that this method has a potential for in-situ monitoring of thin-film deposition or etching. Transient effects are studied in a thin quartz plate and the propagation velocity of thermal waves is measured.Our colleague Martin Nonnenmacher passed away May 1992. We deplore his early death deeply and acknowledge gratefully the excellent cooperation with him.     

Effect of Cr and V dopants on the chemical stability of AZO thin film

The effect of the dopants of Cr and V on the optoelectronic properties of AZO thin film by pulsed DC magnetron sputtering has been investigated. We also use HCl and KOH solutions to conduct the chemical stability of AZO:Cr:V thin film. The experimental results show that the optimum AZO optoelectronic properties without Cr and V doping obtain the resistivity of 9.87 × 10⁻⁴ Ω cm, optical transmittance of 84% and surface roughness rms value of 2.6 nm. The chemical stability of AZO will increase after Cr and V doping. Under the added V = 0.19 wt.%, Cr = 0.56 wt.%, AZO:Cr:V thin film showed 52% increased chemical stability and 128% decrease in surface roughness after etching (the resistivity was 3.62 × 10⁻³ Ω cm and optical transmittance 81%). From the experimental results, the higher resistivity obtained after KOH etching compared with after HCl etching. The reason is that the Zn/Al ratio will reduce after etching and cause the AZO film carrier density to reduce as well. However, the optical transmittance obtained after KOH etching will be higher than that after HCl etching. This is because that a better surface roughness after KOH etching obtained than after HCl etching.     

Wet‐Etching Induced Abnormal Phase Transition in Highly Strained VO2/TiO2 (001) Epitaxial Film

The metal–insulator transition (MIT) behavior in vanadium dioxide (VO₂) epitaxial film is known to be dramatically affected by interfacial stress due to lattice mismatching. For the VO₂/TiO₂ (001) system, there exists a considerable strain in ultra‐thin VO₂ thin film, which shows a lower T_c value close to room temperature. As the VO₂ epitaxial film grows thicker layer‐by‐layer along the “bottom‐up” route, the strain will be gradually relaxed and T_c will increase as well, until the MIT behavior becomes the same as that of bulk material with a T_c of about 68 °C. Whereas, in this study, we find that the VO₂/TiO₂ (001) film thinned by “top‐down” wet‐etching shows an abnormal variation in MIT, which accompanies the potential relaxation of film strain with thinning. It is observed that even when the strained VO₂ film is etched up to several nanometers, the MIT persists, and T_c will increase up to that of bulk material, showing the trend to a stress‐free ultra‐thin VO₂ film. The current findings demonstrate a facial chemical‐etching way to change interfacial strain and modulate the phase transition behavior of ultrathinVO₂ films, which can also be applied to other strained oxide films.     

A glass thinning and texturing method for light incoupling in thin‐film polycrystalline silicon solar cells application

For polycrystalline silicon (poly‐Si) thin‐film solar cells on ～3 mm borosilicate glass, glass thinning reduces the glass absorption and light leaking to neighbouring cells; the glass texturing of the sun‐facing side suppresses reflection. In this Letter, a labour‐free wet etching method is developed to texture and thin the glass at the same time in contrast to conventionally separated labour‐intensive glass thinning and texturing processes. For 2 cm² size poly‐Si thin‐film solar cells on glass superstrate, this wet etching successfully thins down the glass from 3 mm to 0.5 mm to check the ultimate benefit of the process and introduces a large micron texture on the sun‐facing glass surface. The process enhances J_sc by 6.3% on average, with the optimal J_sc enhancement of 8%, better than the value of 4.6% found in the literature. This process also reduces the loss in external quantum efficiency (EQE loss), which is due to light leaking to neighbouring cells, dramatically. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of oxygen plasma treatment on boron carbon nitride film composition

Variations in the composition and bonds of boron carbon nitride (BCN) film caused due to an oxygen (O₂) plasma ashing process are investigated for a low dielectric constant (low-k) insulating film for next generation LSI devices. The O₂ plasma treatment is preformed for BCN samples with various C compositions. The etching rate of BCN films with an O₂ plasma decreases with increasing C composition. The reaction of O atoms is suppressed in the BCN film with a high C composition. B-N and B-C bonds with lower bond energies are easily broken by the O₂ plasma and replaced by the generation of B-O, N-O, and C-O bonds. The B-atom concentration for all samples is decreased significantly by the O₂ plasma treatment. Ion bombardment may play a more dominant role than the O-atom reaction in the etching of the BCN film. The existence of C-N bonds with a high bonding energy may suppress etching and incorporation of O atoms.     

Growth of completely (110)-oriented Pt film on Si (100) by using MgO as a buffer by pulsed laser deposition

(110)-textured MgO films were grown on Si (100) with etching and without etching by pulsed laser deposition. The deposited MgO films were shown to be droplets-free. The MgO film was used as a buffer layer to further grow Pt film on Si (100). A completely (110)-oriented Pt film was obtained on such a buffer layer and its surface is very smooth with a roughness of about 7.5 nm over 5×5 μm. This can be used as a new oriented Pt electrode on silicon for devices. Received: 23 January 2001 / Accepted: 27 April 2001 / Published online: 27 June 2001     

Excimer-laser etching on silicon

Studies have been made of poly- and single Si etching induced by excimer-laser irradiation of the silicon surfaces in halogenated gases. Etching was investigated for different conduction types, impurity concentrations and crystallographic planes. Chlorine atoms accept electrons generated in photoexcited, undoped p-type Si, thus becoming negative ions which are pulled into the Si. However, the n⁺-type Si is etched spontaneously by Cl^– as a result of the availability of conduction electrons. Fluorine atoms, with the highest electronegativity, take in electrons independent of whether the material is n- or p-type. And thus, the easy F^– ion penetration into Si causes spontaneous etching in both types. New anisotropic etching for n⁺ poly-Si is investigated because of its importance to microfabrication technology. Methyl methacrylate (MMA) gas, which reacts with Cl atoms, produces a deposition film on the n⁺ poly-Si surface. The surface, from which the film is removed by KrF (5 eV) laser irradiation, is etched by Cl atoms, while the film remains on the side wall to protect undercutting. However, with the higher photon energy for the ArF (6.4 eV) laser, the Si-OH bonds are broken and electron traps are formed. These electrontrapping centers are easily annealed out in comparison to the plasma-induced centers. Pattern transfer etching for n⁺ poly-Si has been realized using reflective optics. The problems involved in obtaining finer resolution etching are discussed.     

Time-resolved measurements during backside dry etching of fused silica

The laser-induced backside dry etching (LIBDE) investigated in this study makes use of a thin metal film deposited at the backside of a transparent sample to achieve etching of the sample surface. For the time-resolved measurements at LIBDE fused silica samples coated with 125 nm tin were used and the reflected and the transmitted laser intensities were recorded with a temporal resolution of about 1 ns during the etching with a ∼30 ns KrF excimer laser pulse. The laser beam absorption as well as characteristic changes of the reflection of the target surface was calculated in dependence on the laser fluence in the range of 250-2500 mJ/cm² and the pulse number from the temporal variations of the reflection and the transmission. The decrease of the time of a characteristic drop in the reflectivity, which can be explained by the ablation of the metal film, correlates with the developed thermal model. However, the very high absorption after the film ablation probably results in very high temperatures near the surface and presumably in the formation of an absorbing plasma. This plasma may contribute to the etching and the surface modification of the substrate. After the first pulse a remaining absorption of the sample was measured that can be discussed by the redeposition of portions of the ablated metal film or can come from the surface modification in the fused silica sample. These near-surface modifications permit laser etching with the second laser pulse, too.     

Profile calculation of gold nanostructures by dispersed-nanosphere lithography through oblique etching for LSPR applications

Nanosphere lithography is an inexpensive method used to fabricate gold nanostructures on a substrate. Using dispersed-nanosphere lithography, in which the nanospheres are dispersed on a substrate, 2D or 3D nanostructures can be fabricated by obliquely depositing a gold film on the nanospheres and etching the gold film afterward. These nanostructures are tunable and acute, and are thus good emitting elements for the localized surface plasmon resonance applications. So far, for the fabrication of nanostructures on a substrate with dispersed nanospheres, only 2D nanostructures have been reported through perpendicular etching. We report in this paper that the 3D nanostructures fabricated by dispersed-nanosphere lithography are rigid non-conformal structures, and perpendicular gold etching can be expanded to oblique etching, which provides more possibilities for fabricating the gold nanostructures in various shapes. The profiles of gold nanostructures after several varying angle depositions, and their final profiles after perpendicular or oblique etching, are calculated in this paper. Our profile simulations are applicable for nanospheres (or microspheres) within the range of tens of nanometers to tens of micrometers, and are consistent with our fabricated nanostructures observed using scanning electron and atomic force microscopy. Electronic Supplementary Material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

分层蒸镀制备聚酰亚胺自支撑膜及其特性研究

 采用分层蒸镀法,在玻璃基片上依次蒸镀二氨基二苯醚（ODA）和均苯四甲酸二酐（PMDA）两种单体,然后在空气环境中对样品进行不同温度和时间的热亚胺化处理,使二者在交界面上反应生成聚酰亚胺。经加热150 ℃ 1 h然后经350 ℃ 2 h处理的样品,在脱膜后能制备出直径1.8 cm,厚度为100 nm的聚酰亚胺自支撑薄膜。用FTIR测量了自支撑薄膜的红外光谱,特征吸收峰的分析表明薄膜已基本上完全亚胺化。用原子力显微镜分析了浮法玻璃衬底上聚酰亚胺薄膜的表面形貌,结果表明以ODA作为内层制备的膜层表面更光滑平整。     

纳米TiO2叶片状阵列电极的制备及其在染料敏化太阳电池中电子的输运性能

在低温条件下采用定向刻蚀技术, 对金属Ti片表面用H₂O₂溶液进行刻蚀氧化, 制备了垂直生长的纳米TiO₂叶片状阵列薄膜电极. 通过X射线衍射分析表明, 纳米TiO₂叶片状阵列薄膜经500 ℃下烧结1 h后, 从无定型转变为锐钛矿相. 场发射扫描电子显微镜观察表明: 在80 ℃下的H₂O₂溶液刻蚀氧化, 经1 d制备得到的是Ti片表面垂直生长的叶片状阵列, 其形貌均匀且完整地 关键词： 2')" href="#">纳米TiO₂ 叶片状阵列电极 染料敏化太阳电池 电子传输