Effects of halogenated organic solvents on laser-induced backside wet etching of fused silica

Laser-induced backside wet etching of fused silica using a solution of pyrene dissolved in halogenated and non-halogenated solvents is presented. A significant influence of the solvent used on the etch rate and the etched surface appearance was ascertained. The etching of uniform and smooth surfaces with rates of ∼0.1 nm/pulse for laser fluences below 500 mJ/cm² is observed only for halogenated solvents. Furthermore, reduced threshold fluences, only small incubation effects, and a constant etch rate in dependence on the pulse number were found. The experimental data suggest an additional etch process at low laser fluences characterized by the very low etch rate and the smooth etching observed only with halogen-containing solvents. The generation of halogen radicals/compounds close to the heated surface due to the decomposition of the solvent causing the attack of the surface seems the most probable mechanism. PACS 81.65.Cf; 81.05.Kf; 79.20.Ds; 61.80.Ba; 42.55.Lt; 68.45.Da     

Modifying of etching anisotropy of silicon substrates by surface active agents

The influence of alcohol additives on etch rate anisotropy of Si(hkl) planes has been studied. The etching processes were carried out in 3 and 5 M KOH aqueous solutions saturated and non-saturated with alcohols. Isopropanol, 1-propanol and tert-butanol were examined. It has been showed that the etching process cannot be controlled only by the surface tension of the solution. Saturation of the etching solution with alcohols modifies etch rate anisotropy, lowering the ratio of the etch rate of (110) and vicinal planes to the etch rate of (100) plane. The morphology of Si(hkl) planes etched in 3 M KOH solution saturated with tert-butyl alcohol has been studied in detail. Smooth (331) and (221) planes have been achieved in this solution. The (100) plane turned out to be densely covered by hillocks, opposite to the (100) plane etched in weak-alkaline solution saturated with isopropanol. To explain this phenomenon, the mechanism of hillocks formation on Si(100) surface has been proposed.     

Influence of resists on reactive ion etching

In the course of plasma etching we can observe a loading effect, i.e. the etch rate depends on the size of the etched surface exposed to the plasma. This phenomenon was explained according to Mogab by the plasma active etch species depletion via a rapid etch reaction. But there exist more coomplicated systems, for example SiO₂-photoresist SCR17-CHF₃, where the SiO₂ surface can be etched and a polymer layer can grow on the photoresist surface. The etching of SiO₂ is also influenced by different resists in the case of differences in their chemical structure. The degree of electrode coating with a resist influences both the etch rate of the masking layer. This may be used for the control of the etching selectivity in the SiO₂-resist system independently of other process parameters.The author is grateful to Mr. Z. Pokorný for his help in preparing the SiO₂ layers used in all experiments.     

RIE-induced damage and contamination in silicon

Abstract

Reactive ion etching always causes a dynamic radiation effect to crystalline silicon, beacause of an energetic particle bombardment. RIE induced radiation effects are mostly confined to the near surface within a projected range of impinging ions, but point defects, which are highly mobile at room temperatures, can migrate further into the bulk before a damaged surface layer is etched away. Competition between etch rates and damage rates ultimately determines a degree of the RIE damage residue: the slower the etch rate, the heavier the damage may be accumulated at the near surface, eventually leading to amorphization of the surface region. Also, a removal of the surface layer due to etching or sputtering enhances a chemical reaction between a bare surface and incoming radicals. This easily forms a foreign material on the surface which gives rise to a serious contamination problem. A post-cleaning at a low temperature is highly desirable whenever the surface of active devices must be exposed to reactive plasmas.     

Using IR laser radiation for backside etching of fused silica

Laser-induced backside etching of fused silica with gallium as highly absorbing liquid is demonstrated using pulsed infrared laser radiation. The influences of the laser fluence, the pulse number, and the pulse length on the etch rate and the etched surface topography were studied and the results are compared with these of excimer laser etching. The high reflectivity of the fused silica-gallium interface at IR wavelengths results in the measured high threshold fluences for etching of about 3 J/cm² and 7 J/cm² for 18 ns and 73 ns pulses, respectively. For both pulse lengths the etch rate rises almost linearly with laser fluence and reaches a value of 350 and 300 nm/pulse at a laser fluence of about 12 and 28 J/cm², respectively. The etching process is almost free from incubation processes because etching with the first laser pulse and a constant etch rate were observed. The etched surfaces are well-defined with clear edges and a Gaussian-curved, smooth bottom. A roughness of about 1.5 nm rms was measured by AFM at an etch depth of 0.95 μm. The normalization of the etch rates with respect to the reflectivity and the pulse length results in similar etch rates and threshold fluence for the different pulse widths and wavelengths. It is concluded that etching is a thermal process including the laser heating, the materials melting, and the materials etching by mechanical forces. The backside etching of fused silica with IR-Nd:YAG laser can be a promising approach for the industrial usage of the backside etching of a wide range of materials. PACS 81.65.C; 81.05.J; 79.20.D; 61.80.B; 42.55.L     

Optimization of inductively coupled plasma deep etching of GaN and etching damage analysis

Inductively coupled plasma (ICP) etching of GaN with an etching depth up to 4 μm is systemically studied by varying ICP power, RF power and chamber pressure, respectively, which results in etch rates ranging from ∼370 nm/min to 900 nm/min. The surface morphology and damages of the etched surface are characterized by optical microscope, scanning electron microscope, atomic force microscopy, cathodoluminescence mapping and photoluminescence (PL) spectroscopy. Sub-micrometer-scale hexagonal pits and pillars originating from part of the structural defects within the original GaN layer are observed on the etched surface. The density of these surface features varies with etching conditions. Considerable reduction of PL band-edge emission from the etched GaN surface indicates that high-density non-radiative recombination centers are created by ICP etching. The density of these non-radiative recombination centers is found largely dependent on the degree of physical bombardments, which is a strong function of the RF power applied. Finally, a low-surface-damage etch recipe with high ICP power, low RF power, high chamber pressure is suggested.     

Laser-induced high-quality etching of fused silica using a novel aqueous medium

Laser-induced backside wet etching of fused-silica plates using an aqueous solution of naphthalene-1,3,6-trisulfonic acid trisodium salt (Np(SO₃Na)₃) is reported. A KrF excimer laser was employed as a light source. The etch rate varied greatly with the concentration of the solution and the laser fluence. For lower concentration solutions, the etch rate increased linearly with laser fluence. For highly concentrated solutions, however, the etch rate increased abruptly at higher fluence. Well-defined line-and-space and grid micropatterns were fabricated using a low etch rate. The etched surface was as flat as the surface of the virgin plates and the etched pattern was free of debris and microcracks. The formation and propagation of shockwaves and bubbles in the solution during the etch process were monitored. High pressure, as well as the high temperature generated by the photothermal process, plays a key role in the etching process. Received: 8 April 2002 / Accepted: 12 April 2002 / Published online: 19 July 2002     

Surface-science aspects of plasma-assisted etching

Plasma-assisted etching methods have been used in the manufacture of integrated circuits for more than 10 years and yet the surface-science aspects of this technology are poorly understood. The chemistry must be such that the reactive species generated in the plasma react with the surface being etched to form a volatile product. The chemistry is usually dominated by atoms, molecular radicals and low-energy (20–500 eV) positive ions. In microstructure fabrication, the positive ions are accelerated from the plasma towards the etched surface arriving essentially at normal incidence. Thus, the bottom surface of a very small feature being etched is subjected to both energetic ions and reactive neutral species, whereas the sidewalls of the feature are exposed to reactive neutral species only. The role of the energetic ions is primarily to accelerate the reaction between the neutral species and the etched surface (i.e., accelerate the etch rate), thereby reducing the steady-state top-monolayer coverage of the etching species on the etched surface. On the sidewalls, however, the reacting-species coverage is a saturation coverage. The present understanding of some of the surface-science aspects of this complex environment will be summarized, often using the Si-F system as an example, and some phenomena which are not well understood will be described.     

Laser etching of fused silica using an adsorbed toluene layer

A new method for laser etching of transparent materials with a low etch rate and a very good surface quality is demonstrated. It is based on the pulsed UV-laser backside irradiation of a transparent material that is covered with an adsorbed toluene layer. This layer absorbs the laser radiation causing the etching of the solid. The threshold fluence for etching of fused silica amounts to 0.7 J/cm². The constant etch rate of about 1.3 nm/pulse that has been observed in a fluence interval from 2 to 5 J/cm² is evidence of a saturated process. The limited thickness of the adsorbed layer causes the low etch rates and the rate saturation. The etched surface structures have well defined edges and low surface roughness values of down to 0.4 nm rms. PACS 81.65.Cf; 81.05.Kf; 79.20.Ds; 61.80.Ba; 42.55.Lt     

Track recording properties of soda glass detector for accelerated heavy ions

The etch pit diameters of soda glass detector samples exposed to ₅₄ ¹³² Xe-ions of different energies are measured for different etching times after etching the detector in a ‘new etchant’ free of the adverse effect of the etch product layer. The dependence of track diameter on the energy and on the energy loss, dE/dx of ₅₄ ¹³² Xe-ion in soda glass has been presented. The energy resolution of soda glass and the critical angle for etching of fission fragment tracks in glass detectors have also been determined. The maximum etched track length of ₅₄ ¹³² Xe-ion in soda glass has been compared with the theoretical range. The effects of different annealing conditions on bulk etch rate of glass detector and on diameters of ₅₄ ¹³² Xe-ion tracks have been presented. Experimental results show that there is a decrease in track etch rate, etching efficiency and etchable range of ₅₄ ¹³² Xe-ions with annealing. The annealing of oblique tracks shows that the vertical tracks are more stable than the oblique tracks.     

Modification of plasma-etched profiles by sputtering

Two-dimensional etch profiles are modeled for plasma etching. The etch rate dependence on the angle of incidence of the bombarding ions on the etched surface has a sputtering-type yield. The etch profile is advanced in time by an evolution equation for an etch rate proportional to the modified ion energy flux. Approximate analytical expressions for the etch rates are derived as a product of the etch rates in the absence of the sputtering-type yield and a weighting factor that depends on the angle the ion drift velocity makes with the normal to the wafer surface. The weighting factor is determined from experimental measurements of the angular dependence of ion beam etching by sputtering. These etch rates are valid when the ratio of the ion drift speed to the ion thermal speed is large compared to one. The etching is modeled in the ion flux-limited regime for simplicity. The modifications of the shape of etch profiles of a long rectangular trench and a waveguide structure or strip are treated     

Laser-induced back-side wet etching of fused silica with an aqueous solution containing organic molecules

The laser-induced back-side wet etching of fused silica with aqueous solutions of pyranine (8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt) is reported. KrF and XeF excimer lasers were employed as light sources. Well-defined line-and-space and grid micropatterns, free of debris and microcracks, were obtained. Compared with other organic solutions, the aqueous pyranine etching medium etches more slowly but produces a higher quality etched surface. With the KrF laser, the etch rate ranged from 0.02 to 0.12 nm pulse^-1, depending on the dye concentration and the fluence of the laser. The etch rate decreased dramatically when the XeF laser was employed, which was partially attributed to the lower absorption efficiency of the aqueous pyranine solution at the XeF laser wavelength. Received: 20 November 2001 / Accepted: 21 November 2001 / Published online: 2 May 2002     

Macroscopic etch anisotropies and microscopic reaction mechanisms: a micromachined structure for the rapid assay of etchant anisotropy

A new technique for the rapid quantification of orientation-dependent etch rates, which uses micromachined test patterns and optical microscopy, has been developed. The etching of silicon in KOH etchants with and without isopropanol was studied. Etch rates measured with this technique are in good agreement with conventionally measured rates. In most cases, the etch rate anisotropies are well described by a simple model that is based on step-flow etching. Kinetic Monte Carlo simulations of etching were used to test the simple model and to generate approximate morphologies of the etched surfaces. Vicinal Si(110) surfaces display unusual, orientation-dependent etch rates in some etchants; the functional form of the etch rate anisotropy suggests that a morphological transition occurs on these highly reactive faces. In moderately concentrated KOH solutions where isopropanol is readily soluble, the measured etch rate anisotropies suggest that isopropanol stabilizes step-flow etching.     

Effect of gas residence time on the morphology of silicon surface etched in SF6 plasmas

This paper describes the effect of the SF₆ gas residence time on the morphology of silicon (1 0 0) samples etched in a reactive ion etching system. Profilometry and atomic force microscopy techniques were used to characterize the etching process focusing attention on the evolution of the surface morphology. Under the condition of variable pressure and gas flow rate, the decrease of the residence time leads to an increase of the silicon etch rate concomitantly with an increase of the surface roughness. Contrary fact is observed when the gas flow is fixed and the pressure is varied. Here, the increasing of residence time leads to a constant increase of silicon etch rate with small variations in final surface roughness. To better understanding this resident time effect, mass spectrometry analyses were realized during the discharge for both gas flow conditions.     

Backside etching of fused silica with Nd:YAG laser

The laser-induced backside etching of fused silica with gallium as highly absorbing backside absorber using pulsed infrared Nd:YAG laser radiation is demonstrated for the first time. The influence of the laser fluence, the pulse number, and the pulse length on the etch rate and the etched surface topography was studied. The comparable high threshold fluences of about 3 and 7 J/cm² for 18 and 73 ns pulses, respectively, are caused by the high reflectivity of the fused silica-gallium interface and the high thermal conductivity of gallium. For the 18 and 73 ns long pulses the etch rate rises almost linearly with the laser fluence and reaches a value of 350 and 300 nm/pulse at a laser fluence of about 12 and 28 J/cm², respectively. Incubation processes are almost absent because etching is already observed with the first laser pulse at all etch conditions and the etch rate is constant up to 30 pulses.The etched grooves are Gaussian-curved and show well-defined edges and a smooth bottom. The roughness measured by interference microscopy was 1.5 nm rms at an etch depth of 0.6 μm. The laser-induced backside etching with gallium is a promising approach for the industrial application of the backside etching technique with IR Nd:YAG laser.     

Effects of stirring on the bulk etch rate of CR-39 detector

It is well established that the bulk etch rates for solid state nuclear track detectors are affected by the concentration and the temperature of the etchant. Recently, we found that the bulk etch rate for the LR 115 detector to be affected by stirring during etching. In the present work, the effects of stirring on the bulk etch rate of the CR-39 detector is investigated. One set of sample was etched under continuous stirring by a magnetic stirrer at 70°C in a 6.25 N NaOH solution, while the other set of samples was etched without the magnetic stirrer. After etching, the bulk etch thickness was measured using Form Talysurf PGI (Taylor Hobson, Leicester, England). It was found that magnetic stirring did not affect the bulk etch of the CR-39 detector, which was in contrast to the results for the LR 115 detector.     

Effects of nitrogen addition on methane-based ECR plasma etching of gallium nitride

The effects of nitrogen addition on methane-based ECR plasma etching of GaN were studied. The etch rate 30 nm/min and r.m.s. roughness 2.6 nm were obtained when the GaN sample was etched by a methane-based gas mixture without N₂. The addition of N₂ gas resulted in a decrease of etch rate and a smoother etched surface. The r.m.s. roughness became less than 0.4 nm even only 1.5 sccm N₂ gas was added to the mixture. In situ XPS measurements showed that, without N₂, heavy N-depletion took place on the etched surface, resulting in appearance of Ga metal on the surface. In contrast, the loss of N was compensated when the N₂ gas was added, and the etched surface approached the stoichiometric one with the increase of N₂ gas flow. This suppression of preferential loss of N was considered to be the main reason that improved the etched surface morphology.     

单晶硅表面金字塔生长过程的实验研究

在普通碱液中添加一种特殊的添加剂,在不同时间下对单晶硅表面进行刻蚀.用扫描电子显微镜观察样品表面形貌,结果显示：单晶硅片放入加入添加剂2 mL的刻蚀液中,经过10 min刻蚀后晶体表面零星出现大小不一的金字塔,并有大面积的平滑区|刻蚀15 min后金字塔大小趋向一致,平滑区面积缩小|刻蚀20 min硅片表面形成平均尺寸为2～4 μm金字塔绒面结构,并且均匀性好、覆盖率高|刻蚀25 min后,进入过腐蚀阶段,金字塔出现变大的现象.研究表明：与传统碱腐蚀相比,添加剂可以缩短单晶硅刻蚀时间,并获得较为理想的绒面结构,在工业上应用可以降低生产成本和生产时间,提高生产率.     

The effect of hydrogen as an additive in reactive ion etching of GaAs for obtaining polished surface

The effect of hydrogen on the reactive ion etching (RIE) of GaAs in the CF₂Cl₂ plasma is discussed. The addition of hydrogen into the reaction mixture improves the sharpness of etch borders; the etched surface is smooth for etching depth > 1 μm, etching rate is time-constant.     

Laser-assisted etching of gallium arsenide in chlorine at 308 nm

Xenon chloride (308 nm) excimer laser-assisted etching of GaAs (100) in Cl₂ was demonstrated and characterized with respect to laser and gas parameters. The etch rate increased linearly with laser fluence from thresholds in the range of 50 to 75 mJ/cm² to the highest fluence studied, 650 mJ/cm². For a laser fluence of 370 mJ/cm², the etch rate varied with Cl₂ pressure reaching a maximum at a Cl₂ pressure of about 2 Torr. The etch rate decreased monotonically with Ar buffer gas pressure because of redeposition of GaCl₃ products into the etched channel. The redeposited GaCl₃ affected the etch rate and the etch morphology. The etch rate and morphology also varied with laser repetition rate. The mobility of chlorine on the surface also plays an important role in the etching mechanism.