Rapid thermal annealing of electrically-active defects in virgin and implanted silicon

Chemical etching of single-crystalline (100)Si induced by pulsed laser irradiation at 308, 423, and 583 nm has been investigated as a function of the laser fluence and C1₂ pressure. Without laser-induced surface melting, etching requires Cl radicals which are produced only at laser wavelengths below 500 nm. With low laser fluences ((308 nm)<100 mJ/cm²) etching is non-thermal and based on direct interactions between photocarriers and Cl radicals. For fluences which induce surface melting ((308 nm)>440 mJ/cm²) etching is thermally activated. In the intermediate region both thermal and non-thermal mechanisms contribute to the etch rate.     

Laser projection-patterned etching of (100) GaAs by gaseous HCl and CH3Cl

Laser projection-patterned etching of GaAs in a HCl and CH₃Cl atmosphere performed using a pulsed KrF-excimer laser (=248 nm, =15 ns) and deep-UV projection optics (resolution 2 m) is reported. The etching process carried out in a vacuum system having a base pressure of 10^–6 mbar is shown to result from a purely thermochemical reaction. Etching takes place in two steps: (i) between the laser pulses, the etchant gas reacts with the GaAs surface-atomic layer to form chlorination products (mainly As and Ga monochlorides), (ii) local laser surface heating results in the desorption of these products allowing further reaction of the gas with the surface. The influence of the etching parameters (laser energy density, gas pressure and pulse repetition rate) on the etch rate and the morphology of the etched features was studied. Etch rates up to 0.15 nm per pulse, corresponding to the removal of 0.5 GaAs molecular layer, are achieved. The spatial resolution of the etching process is shown to be controlled by the heat spread in the semiconductor and by the nonlinear dependence of the etch rate on the surface temperature. As a result, etched features smaller or larger than the projected features of the photomask are achieved depending on the laser energy density. Etched lines having a width of 1.3 m were obtained at low fluences by the projection of 2 m wide lines onto the GaAs surface.     

Laser-induced dry chemical etching of Mn-Zn ferrite in CCl2F2 atmosphere

Maskless etching of Mn-Zn ferrite in dichlorodifluoromethane (CCl₂F₂) by Ar⁺-ion laser (514.5 nm line) irradiation has been investigated to obtain high etching rates and aspect-ratio of etched grooves. The etching reaction was found to be thermochemical. High etching rates of up to 360 m/s, which is about one order of magnitude higher than that in a CCl₄ gas atmosphere and even higher than that in a H₃PO₄ solution, have been achieved. A maximum aspect-ratio of 6.9 was obtained.     

Sputtering of solid argon by keV electrons

Thermochemical maskless etching of compound semiconductors (GaAs, InP, InSb, and GaP) has been performed by focused Ar-laser irradiation in chloride gas atmospheres. A controlled minimum linewidth of down to 0.6 m with a maximum etching rate of up to 13 m/s has been obtained. Minimum laser powers necessary for thermochemical etching in each of compound semiconductors were found to be 0.24, 0.56, and 0.06 W, corresponding to minimum local temperature rises of 190, 515, and 110°C for GaAs, InP, and InSb, respectively. Etching rates exhibited Arrhenius behavior with activation energies of 3.6–3.9 kcal/mole. Etching at excessively higher laser powers than those minimum powers was found, by microprobe photoluminescence measurements, to degrade the optical quality of the etched substrate.     

Laser-induced chemical etching of silicon in NF3 atmosphere

Chemical etching of single-crystal Si in an NF₃ atmosphere is performed by continuous irradiation with an Ar⁺ laser at 514.5 nm. The etching process proves to be a thermally stimulated chemical reaction between solid Si and NF₃ gas. The experimental results show how the depth and width of the etched grooves depend on laser power, scan speed, and gas pressure. The etch rates observed may exceed 25 m/s.     

XeCl laser controlled chemical etching of aluminum in chlorine gas

The 308 nm XeCl laser assisted etching process of thin Al metal films on Si substrate in Cl₂ gas was investigated. Etch rates were measured versus the laser fluence on the sample, the laser repetition rate, the Cl₂ pressure and the sample temperature. Irradiation experiments under vacuum of films which were previously exposed to Cl₂, and laser assisted etching in rare gases, nitrogen and air mixtures with Cl₂ were also performed to elucidate the mechanism of the etching process. The surface morphology was investigated by scanning electron microscopy. The results show that a) Etch rates of up to about 1.5 m per pulse are obtained which are strongly dependent on the Cl₂ pressure and sample temperature. b) The etching mechanism is essentially a chemical chlorination of the Al in between the laser pulses which is followed by photo-ablation of the reaction products, c) AlCl₃ evaporation and redeposition processes can explain the observed results. d) The Al films can be etched fully and cleanly without damage to the smooth Si substrate. e) Etching through adjacent or imaged mask on the Al film yielded relatively smooth and well defined Al walls with structures of the order of 1 m.     

Thermochemical dry etching of single crystal ferrite by laser irradiation in CCl4 gas atmosphere

Single crystal ferrite has been etched by focused Ar⁺ laser irradiation in a CCl₄ gas atmosphere. The etched groove showed cracks due to thermal stresses when samples were etched by a laser vaporization process in a vacuum, while in a CCl₄ atmosphere, such cracks were not observed. An etching rate of 68 /s obtained for a thermochemical process by laser irradiation was four orders of magnitude higher than that for a wet chemical etching process. A high aspect (depth-to-width) ratio of up to 10 was obtained for etched grooves. Under specific conditions, bending of the groove and orientation dependence in etching rate were observed.     

InGaAsP/InP 1.55-μm lasers with chemically assisted ion beam-etched facets

Chemically assisted ion beam etching (CAIBE) involving an Ar ion beam and a halogen ambient gas (Cl₂, IBr₃) has been used to etch high-quality laser facets for InGaAsP/InP bulk lasers (1.55 m). We achieved eich rates of 40.0–75.0 nm min^–1 at substrate temperatures between-5 and +10°C. These low temperatures have allowed us to utilize UV-baked photoresists as well as PMMA as etch masks, facilitating very simple process development. Higher substrate temperatures (50 to 120°C) yield still higher etch rates, but at the expense of severely degraded surface morphologies. Angle resolved x-ray photoelectron spectroscopy (XPS) was investigated for observing etched InP surfaces. A disproportioned surface has been detected after etching in the higher temperature range; low temperatures yield stoichiometric surfaces.     

Ar ion laser assisted chemical etching of via holes in tungsten sheets in air

Ar ion laser assisted chemical etching of 150 m thick annealed tungsten sheets in air is reported. The material removal mechanism involves local heating by the laser to temperatures in the range of 1000–1500 °C that causes rapid oxidation of the W to WO₃ which volatilizes readily. Holes with straight walls and slightly enlarged entrances near the surface were drilled with etch rates as high as 11.5 m/s at 13.8 W, and a minimum hole diameter of 21 m at 8.1 W. The diameters of the holes and the etch rates were measured and found to increase as a function of the laser power. It was found that by increasing the laser power above 11–12 W, no change was observed in the hole diameters which remained constant at about 31 m, whereas the etch rates continued to increase even faster than at low powers. Distinct adjacent holes of 25 m diameter could be drilled with their centers separated by as little as 60 m. This is therefore also the etching resolution in the present study.     

Laser-induced backside wet etching of fluoride and sapphire using picosecond laser pulses

Laser-induced backside wet etching (LIBWE) is a promising process for microstructuring of rigid chemical resistant and inert transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated in a number of studies. LIBWE in a time scale of femtosecond and picosecond pulse durations has been investigated only in a few studies and just on fused silica. In the present study LIBWE of fluorides (CaF₂, MgF₂) and sapphire with a mode-locked picosecond (t _p=10 ps) laser at a UV wavelength of λ=355 nm using toluene as absorbing liquid has been demonstrated. The influence of the laser fluence and the pulse number on the etching rate and the achieved surface morphology was investigated. The etching rate grows linearly with the laser fluence in the low and high-fluence ranges with different slopes. The achieved etching rates for CaF₂ and for sapphire were in the same range. Contrary to CaF₂ and sapphire the etching rates of MgF₂ were one magnitude less. For backside etching on sapphire at high fluences smooth surfaces and at low fluences ripples pattern were found, whereas fluoride surfaces showed a trend towards crack formation.     

Dry‐etching‐assisted femtosecond laser machining

Femtosecond laser machining has been widely used for fabricating arbitrary 2.5 dimensional (2.5D) structures. However, it suffers from the problems of low fabrication efficiency and high surface roughness when processing hard materials. To solve these problems, we propose a dry‐etching‐assisted femtosecond laser machining (DE‐FsLM) approach in this paper. The fabrication efficiency could be significantly improved for the formation of complicated 2.5D structures, as the power required for the laser modification of materials is lower than that required for laser ablation. Furthermore, the surface roughness defined by the root‐mean‐square improved by an order of magnitude because of the flat interfaces of laser‐modified regions and untreated areas as well as accurate control during the dry‐etching process. As the dry‐etching system is compatible with the IC fabrication process, the DE‐FsLM technology shows great potential for application in the device integration processing industry.

     

Wet-chemical etching of Mn-Zn ferrite by focused Ar+-laser irradiation in H3PO4

Maskless etching of Mn-Zn ferrite in H₃PO₄ aqueous solution by Ar⁺-ion laser irradiation has been investigated to obtain high etching rates and aspect-ratios of etched grooves. The etching processes have been found to be photochemical in the low laser power region and thermochemical in the high laser power region. High etching rates of up to 340 μm/s and an aspect-ratio of 30 for slab structures have been achieved. In the case of high aspect-ratio structure, the etching rate was limited by the low diffusion efficiency of etched products in the etchant. Periodic ripple structures have been observed under specific etching conditions.     

Laser generated microstructures

Deposition and etching processes based on the interaction of laser light with a substrate surface and molecules of the surrounding ambient are discussed in this tutorial review. This laser writing approach is based on photolytic, pyrolytic, or photoelectrochemical microreactions. The fundamental properties of such reactions and corresponding processing parameters (e.g. deposition or etch rate, resolution) are discussed. Important published results for deposition by photolysis, pyrolysis, and etching are summarized in the form of tables. A special list of potential applications for such techniques and a list of all materials used thus far for laser deposition and etching are included.     

Effect of composition gradient on CuIn3Te5 single-crystal properties and micro-Raman and infrared spectroscopies

The topography and roughness evolution of surfaces etched by laser-induced backside wet etching (LIBWE) is investigated in detail. The etching of sub-m gratings with a period of 760 nm into flat surfaces by means of interfering laser beams shows a saturation of the grating depth within 20 pulses. The over-etching of already microstructured surfaces results in the change of the cross section and in reduction of the microstructure height with increasing pulse number. The decrease in height of sub-micron gratings from 125 to less than 10 nm within 15 laser pulses causes a substantial roughness reduction. The depth limitations in etching of the gratings as well as the height reduction of microstructures are the result of the influence of the surface topography to the heat flow. The more efficient heating of surface peaks in contrast to the valleys results in higher etch rates and probably causes the smooth surfaces observed in LIBWE processing. The thermal diffusion length determines the structure dimension influenced by this smoothing effect. PACS 81.65.Cf; 81.05.Je; 42.70.Ce; 42.55.Lt     

Direct observation of laser-induced crystallization of a-C:H films

The post-growth modification of diamond-like amorphous hydrogenated carbon a-C:H films by laser treatment has been studied by transmission electron microscopy and Raman spectroscopy. a-C:H films grown on Si substrates by benzene decomposition in a rf glow discharge were irradiated with 15 ns pulses of a KrF-excimer laser with fluences in the range of E=50–700 mJ/cm². At fluences below 100 mJ/cm² an increase in the number of graphitic clusters and in their ordering was evidenced from Raman spectra, while the film structure remained amorphous according to electron microscopy and electron diffraction observations. At higher fluences the appearance of diamond particles of 2–7 nm size, embedded into the lower crystallized graphitic matrix, was observed and simultaneously a progressive growth of graphite nanocrystals with dimensions from 2 nm to 4 nm was deduced from Raman measurements. The maximum thickness of the crystallized surface layer (400 nm) and the degree of laser annealing are limited by the film ablation which starts at E>250 mJ/cm². The laser-treated areas lose their chemical inertness. In particular, chemical etching in chromium acid becomes possible, which may be used for patterning the highly inert carbon films.     

Laser-induced chemical etching of ceramic PbTi1−xZrxO3

The laser-induced etching of ceramic PbTi_1–xZr_xO₃ in a hydrogen atmosphere and in air has been investigated. Visible Ar⁺ and Kr⁺ laser radiation was employed in most of the experiments. In H₂ atmosphere, regular patterning of the ceramic is possible. Average etch rates reach up to about 250 m/s.     

Maskless photoassisted etching of N-type Ga0.47In0.53As in basic solutions

The maskless photoassisted etching of n-type Ga_0.47In_0.53As is examined for basic KOH solutions in comparison with GaAs and InP material. The etch rate increases with laser intensity and with carrier concentration up to a saturation value. The best etch rate is obtained with molar KOH in ethyl alcohol (7 ms^–1 for laser intensity 10⁴ W cm^–2). Selective etching have been realized on heterojunction in order to isolate p-n junctions without the help of masks.     

Laser-induced etching of titanium by Br2 and CCl3Br at 248 nm

A quartz crystal microbalance (QCM) has been used to study the KrF* excimer laser-induced etching of titanium by bromine-containing compounds. The experiment consists of focusing the pulsed UV laser beam at normal incidence onto the surface of a quartz crystal coated with 1 m of polycrystalline titanium. The removal of titanium from the surface is monitored in real time by measuring the change in the frequency of the quartz crystal. The dependence of the etch rate on etchant pressure and laser fluence was measured and found to be consistent with a two-step etching mechanism. The initial step in the etching of titanium is reaction between the etchant and the surface to form the etch product between laser pulses. The etch product is subsequently removed from the surface during the laser pulse via a laser-induced thermal desorption process. The maximum etch rate obtained in this work was 6.2 Å-pulse^–1, indicating that between two and three atomic layers of Ti can be removed per laser pulse. The energy required for desorption of the etch product is calculated to be 172 kJ-mole^–1, which is consistent with the sublimation enthalpy of TiBr₂ (168 kJ-mole^–1). The proposed product in the etching of titanium by Br₂ and CCl₃Br is thus TiBr₂. In the etching of Ti by Br₂, formation of TiBr₂ proceeds predominantly through the dissociative chemisorption of Br₂. In the case of etching with CCl₃Br, TiBr₂ is formed via chemisorption of Br atoms produced in the gas-phase photodissociation of CCl₃Br.     

Photokinetic etching of polyethylene terephthalate films by continuous wave ultraviolet laser radiation

Continuous wave laser radiation from an argonion laser in the wavelength range 275–330 nm can be used to etch polyethylene terephthalate (PET) films with as little thermal damage as from a pulsed, ultraviolet laser (248 nm or 308 nm) provided the beam is focussed to a spot of 10–100 kW/cm² of power density and is moved over the surface at speeds at which the transit time over its own diameter (which can be looked upon as a pulse width) is on the order of 10–200 s. In contrast to results which had been obtained previously on the photokinetic etching of polyimide and doped polymethyl methacrylate films under similar conditions, the sensitivity of PET to etching is >5-fold greater than either of these polymers and increases steadily with increasing pulse width. There is lateral thermal damage as the pulse widths increase to >200 s. The material that is removed is vaporized in part. More than 20% is probably ejected in a molten state and resolidifies at the edge of the cut. There is no acoustic report similar to that seen in ablative photodecomposition. The process appears to be largely thermal in nature.     

Fabrication of ordered arrays of silicon cones by optical diffraction in ultrafast laser etching with SF<Subscript>6</Subscript>

We report the fabrication of ordered rows of conical spikes on a Si(111) substrate by etching with a femtosecond pulsed laser in the presence of SF₆ gas. This is achieved by the creation of an optical near-field diffraction pattern when a copper wire (diameter 140 m) is placed on the surface. Measurements of the height, base width and average separation of the silicon cones at two irradiation wavelengths (780 nm and 390 nm) confirm the important role of the optical parameters in the photochemical etching process. Moreover, the dependence of average cone separation on the laser repetition rate indicates that long-timescale processes such as post-pulse chemical interactions are important in cone formation. PACS 61.30.Hn; 61.82.Fk; 61.80.-x; 42.25.Bs; 78.20.-c