WO2002060828A2 - Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces - Google Patents
Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces Download PDFInfo
- Publication number
- WO2002060828A2 WO2002060828A2 PCT/US2002/002507 US0202507W WO02060828A2 WO 2002060828 A2 WO2002060828 A2 WO 2002060828A2 US 0202507 W US0202507 W US 0202507W WO 02060828 A2 WO02060828 A2 WO 02060828A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plasma
- shaping
- workpiece
- damage
- reactive
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/206—Cleaning
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/047—Coating on selected surface areas, e.g. using masks using irradiation by energy or particles
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
- H05H1/00—Generating plasma; Handling plasma
- H05H1/24—Generating plasma
- H05H1/26—Plasma torches
- H05H1/30—Plasma torches using applied electromagnetic fields, e.g. high frequency or microwave energy
Definitions
- the field of the invention relates to shaping surfaces using a gas plasma.
- Plasma etching at reduced pressure is extensively used in the semiconductor industry for processing of a wide variety of materials including semiconductors, metals and glasses (1 ).
- the references cited herein are listed as end notes and are all incorporated by reference. Removal mechanisms and removal rates have been studied extensively and are reasonably well understood. With pressures in the 10 to 20 millitorr range, ion and electron densities are on the order of 10 9 to 10 10 cm "2 . These reactive ions are believed responsible for the majority of material removal. Consequently, the technique is known as reactive ion etch (RIE). With electron energies in the 3 to 30 eV range, material removal tends to be largely chemical in nature. Below 50 eV physical sputtering is negligible and subsurface damage is nonexistent. In the absence of sputtering, reaction products must be volatile or the process is self terminating after the formation of the first product layer.
- a major limitation of the capacitively coupled discharge is the requirement that the workpiece be either conductive or less than 10 mm thick.
- etch rates were noted to be dependant on part thickness decreasing by a factor of ten when thickness changed from 2 to 10 mm. Above 10 mm the rates were too low to be of much use (20 nm / min) (4).
- Optics up to 188 mm in diameter with 30° of slope were polished under mild vacuum. With metrology used in an iterative procedure, the chamber is vented and pumped down for the next etch step.
- Ion beam sputtering or neutral ion beam milling removes material from the surface of the workpiece by kinetic interaction of ions with atoms or molecules of the surface.
- the technique has been around for quite a while (6) and the main application has been optical polishing for fused silica optics (7, 8).
- Earliest sources used beams with energies that were a large fraction of an MeV, while most recent systems use Kaufman sources with energies of 1500eV to providing the optimum sputter yield.
- DCP direct current plasma
- a device capable of thinning wafers (12).
- the system called a “Plasma Jet”
- argon as the plasma gas with a trace amount of fluorine or chlorine for reactive atom production.
- the main intent of the device is to do backside thinning of processed silicon wafers for smart card and other consumer applications.
- the industry requirement of a 200 mm wafer with a thickness less than 50 um cannot be met with any current polishing process.
- the defects and microcracks introduced by abrasive systems create a damage layer that is a large fraction of the desired 50 um thickness.
- Thin wafers produced by polishing are prone to fracture even with delicate handling.
- wafers are thinned in a batch mode by placing them on a platten and using planetary type motion to move the sub-aperture plasma in a pseudo random fashion across the surface.
- the discharge is about 1" in diameter and the removal rate is 0 to 20 mm / min for a 200 mm wafer with a uniformity of ⁇ 5 %.
- Total material removal comes to about 30 cm 3 / hr.
- the DC plasma In its current configuration, the DC plasma is not well suited for aspheric generation or material deposition.
- the trace reactants are introduced along with the bulk gas and, as a consequence, are widely distributed across the discharge, substantially increasing the footprint and the minimum feature size. Electrodes that are used to establish the arc are eroded by the reactants and add particulates to the atom stream; not a problem when material removal is the primary concern and surface roughness is not an issue. Electrode erosion also causes fluctuations in plasma conditions and accounts for the reduced uniformity compared to RIE systems. Detrimental electrode reactions also preclude the use of oxygen and many other plasma gases. Finally, the discharge is not as hot as an ICP and, as a result, the production of reactant atoms is reduced.
- a radio frequency (RF) plasma has been used to slice silicon and as a sub- aperture tool to polish optics (13-15).
- the plasma is generated around a wire or blade electrode immersed in a noble gas atmosphere that contains a trace of reactive components.
- the plasma converts the reactive precursors to radical atoms that react chemically with the workpiece, removing material one atom at a time.
- CVM chemical vapor machining
- the electrode is brought to within 200 microns of the workpiece wherever material is to be eroded. Analysis has shown the resulting surfaces to be damage free and the process is considered to be entirely chemical in nature.
- a comparison of damage in silicon for polishing, sputtering, chemical vapor machining and chemical etching is reported in the literature (13).
- one object of the invention is the removal of material with no continuing roughening of or damage to the material.
- Another object of the invention is a wide range of material removal, from one or two layers of atoms at a time to thousands of times the normal etch rate of known techniques.
- the present invention significantly improves the capabilities of precision manufacturing technology.
- the invention provides method and apparatus that can remove damage introduced by previous process steps, figure highly aspheric optics or precision components and reduce high frequency surface roughness.
- the invention functions as a shaping and a finishing operation in both the subtractive and the additive mode.
- Subsurface damage in the form of cracks and plastically deformed material are removed in a dry etch process. Removal rates are very high and large workpieces can be quickly configured without a vacuum or the requirement of any special atmosphere.
- the proposed process is operated primarily in a subtractive manner and does not leave behind a contaminated redeposition layer as a final surface.
- An object of the invention is a method and apparatus that can be tuned to produce a deterministic and highly asymmetric surface in a single operation from a data file in either the subtractive or the additive mode.
- Final shaping of optics and precision surfaces is executed by exposing the workpiece to reactive atoms generated by an atmospheric pressure, inert gas, inductively coupled plasma discharge (ICP).
- ICP inductively coupled plasma discharge
- the plume of the plasma is stable, the reproducible and functions as a sub-aperture tool.
- the plume has a stable distribution of reactive gases. Reactants are created from trace gases introduced into the discharge and are chosen to fit the chemistry of the workpiece. Material removal mechanisms are almost entirely chemical and reactive gases are chosen to produce volatile reaction products that leave the surface area without assistance.
- the plasma footprint is highly reproducible, resulting in predicable removal rates over large areas.
- Figure 1 shows an embodiment of a plasma torch used to configure a workpiece
- Figure 2 shows the distribution of ions and atoms in the discharge of the plasma torch of Figure 1.
- Figure 3 is a schematic of an embodiment of the invention depicting the overall system.
- Figure 4 is a schematic depicting an embodiment of the torch box and sample box of the embodiment of Figure 3.
- Figure 5 is a profilometer trace of an etch pit made with an embodiment of a static plasma system of the invention depicting the footprint produced with a particular set of plasma conditions and a specific dwell time.
- Figure 6 is a 3-dimensional interferomteric view of an etch pit made with an embodiment of a static plasma system of the invention depicting the footprint produced with a particular set of plasma conditions and a specific dwell time.
- Figure 7 is a chart of the material removal from a specimen versus the gas flow rate for a specific example.
- Figure 8 is a chart showing, for one example, the amount of removal of material from a specimen versus the distance of the plasma from the specimen.
- Figure 9 is a graph depicting the reaction efficiency of a sample reaction versus the gas flow rate.
- Figure 10 is a chart depicting the effect of the distance of the plasma from the specimen on the efficiency of the process for a specific example.
- Figure 1 shows a plasma torch with three types of gas flow and the location of the plasma relative to the load coil.
- This torch is used to configure the workpiece shown.
- a two tube torch design with an outer (plasma gas) and a central tube will function in an identical manner.
- the auxiliary tube functions only to adjust the position of the plasma within the load coils to a small degree.
- the current from a 13.56 MHz or a 27.12 MHZ RF generator flows through a three turn copper load coil around the top of the torch.
- the energy is coupled into the plasma through a cylindrical skin region that is located on the outer edge of the discharge nearest the load coil.
- a long outer tube on the torch can be used to cool down the reactive gases while keeping out quenching species from the air (such as nitrogen, oxygen or water vapor).
- the plasma is supported in a quartz tube by the plasma gas which introduced tangentially to form a stabilizing vortex.
- Workpiece material is removed by reaction with reactive species created in the plasma by dissociation of a non-reactive precursor usually introduced in the form of a gas.
- the precursor can also exists as an aerosol or small particles suspended in the host gas.
- the precursor is typically introduced into the central tube of the torch facilitating penetration into the center of the discharge.
- the plasma skin is thin in this region and the precursor easily penetrates the thermal gradient presented by the excited argon atoms. If the precursor is in the form of a gas it can be introduced into the plasma with the plasma gas resulting in a wider etching footprint.
- the plasma is supported in a quartz tube by the plasma gas which is introduced tangentially to form a stabilizing vortex.
- the method and apparatus of the atmospheric pressure inert gas plasma device produces reactive neutral species over a limited area and permits controlled chemical erosion of material at a rate of more than 500 um / min.
- the technique offers several advantages over previous reactive sources for ion-type milling and is a non- contact type shaper / polisher capable of material removal by chemical means.
- the concentration of reactive species is much higher than reduced pressure systems and removal rates are at least 1000X over RIE and other similar approaches.
- the system is also capable of removal rates as low as a few layers of atoms at a time. Without the need for a vacuum or environmental chamber, there is no practical limit to workpiece size and the process is easily compatible with a number of in-situ metrology techniques.
- the system includes a RF ICP generator and impedance matching network used to produce reactive atoms.
- Initial sample materials included single crystal silicon (several orientations), fused silica, diamond and silicon carbide.
- the workpieces 114 ( Figure 4) were held in a vacuum chuck (116) and could be rotated with a rotating stage (108) and translated with a translating stage (110) across the discharge.
- An additional stage (112) was used to control the distance of the sample to the discharge.
- the shape and symmetry of the static footprint was measured as a function of plasma power (between 0J5 and 2.5 kW), primary argon gas flow rates (from 5 to 25 L / min), type and concentration of reactive species, discharge size (plasma diameter controlled by the size of outer tube), distance from the plasma and dwell time. With changes in the above parameters, the footprint was found to vary in a predicable fashion. [0044] The footprint depth and width was measured by tracing the etch pit with a stylus profilometer. Material removal could be calculated from the measured size of the pit and compared to the weight of the material lost by the sample during exposure to the plasma. Material removal rates for two plasma parameters are detailed in Figures 7 and 8.
- a typical footprint with the reactive gas introduced into the center of the plasma is shown in figure 5.
- a Fizeau type interferometer was also used to determine the overall symmetry of the etch pit (Figure 6).
- the footprint is Gaussian in nature and has a full width at half maximum equal to 1.0 X the inner diameter of the outer torch tube.
- the width of the footprint is effected only slightly by moderate changes in plasma operating conditions such as power and gas flow rate. As distance from the plasma increases the area of the reactive species and the resulting pattern of material removal tends to broaden.
- the depth of the footprint is related to distance from the discharge, flow rate of reactive species, power of the plasma and dwell time and varies in a linear fashion over a limited range of operating conditions.
- sample results there was material removal without continuing roughening of or damage to the specimen.
- the surface structure of the workpiece was studied with atomic force microscopy (AFM) at several different etch depths.
- a survey of an etch pit from the edge to the center revealed the presence of subsurface structure indicative of damage that remained from previous processing steps.
- a survey of an etch pit from the edge to the center revealed the presence of subsurface structure indicative of damage that remained from previous processing steps.
- AFM is also used to monitor the change of surface roughness as a function of experimental parameters. Specifically, power spectral densities (PSD) is measured to determine the effect the etching process has on the type of roughness.
- PSD power spectral densities
- a typically surface for a plasma polished fused silica optic is 0.3 nm Ra as measured with an AFM. Roughnesses as low as 0.1 nm were occasionally obtained.
- the plasma is not only a static removal tool, but also a deposition source. Emission or absorption spectroscopy are used to determine the composition of the plasma far downstream. Prior work has suggested that the optimum distance from the discharge is between 380 mm (15) and 600 mm (16). The range of optimum deposition for a particular species is quite narrow and can depend more on physical factors such as temperature than on chemical state or structure. As a result, knowledge of structural, chemical and physical properties of the atoms in the discharge are determined spectroscopically.
- a unique application of the system is, for example, to polish single crystal diamond tools for SPDT (single point diamond turning).
- SPDT single point diamond turning
- the vast majority of tools are currently made with abrasive processes. This leads to a damaged layer on the surface of the diamond that degrades the performance of the tool.
- tools must be used for an unspecified break-in period before they produce their best surfaces.
- the break-in period merely amounts to polishing of the tool by the work piece; a poorly controlled process at best.
- Plasma etching removes the damage layer without propagation of surface fractures or introducing any additional stress into the tool.
- the results are a stronger, longer lasting tool with superior performance.
- Presently chemically polished tools are available; but, a peculiarity of the process is a rounded cutting edge. This radius is crucial to the performance of the tool and should be kept as small as possible, ideally under 1 nm.
- the plasma process does not result in any increase in the radius and, in fact, was used to slightly modify the rak
- the plasma polishing aspect of the invention is part of the precision engineering core competency enabling the production of precision components with a high degree of surface quality and integrity for a wide variety of applications. It can be a key shaping and finishing technology for many products, well beyond the application in optics described herein.
- the plasma chemistry can be tailored to remove heterogenous materials such as AITiC, a composite ceramic composed of aluminum oxide and titanium carbide.
- AITiC a composite ceramic composed of aluminum oxide and titanium carbide.
- the ability to shape refractory materials such as silicon carbide at high speed without the use of abrasives is a very important industrial application. The relevance to all programs that rely on precision fabricated equipment is clear.
- a straightforward application of plasma polishing is the fabrication of large, damage-free, low scatter, aspheric silicon mirrors and lenses.
- Germanium while inferior to silicon in terms of strength and cost is currently used because it can be shaped with greater ease.
- the plasma process permits the substitution of silicon for germanium in infrared optics and windows. A number of applications for these specialized visible and infrared optics currently exists within several branches of the government and in the defense industry.
- An example of an important first application for this technology is the fabrication of a large (50" dia.) single crystal silicon mirror for a space based telescope.
- the mirror Prior to polishing, the mirror is single point diamond turned (SPDT) to the correct dimensions.
- SPDT single point diamond turned
- a certain degree of subsurface damage is inherent in the SPDT process.
- the damage layer can be as deep as 10 um. It is extremely difficult to remove this much material with standard polishing process while minimizing figure error.
- the figuring capabilities of the plasma process will be able to correct the surface of the optic while removing as much material as necessary to eliminate the damage layer. This is a clear situation where a vacuum chamber capable of handling a 50" optic would be an impediment to fabrication if the choice of process was PACE or ion beam machining.
- NIF National Ignition Facility
- Superior, high damage threshold optics and debris shields would be available for NIF at a decreased cost due to the simplification of the final figuring and polishing step.
- High material removal rates would increase through-put while producing a parts with no subsurface damage and improved finish and figure.
- a more pragmatic use would be the in-situ repair of some optics for the new laser.
- Renewable components such as debris shields can be refinished rapidly in an on-site facility reducing the overall number of pieces in the pipeline. Cracks can be removed and new material deposited in the defect area.
- fused silica optics material would be removed with the addition of CF 4 to he plasma following the reaction:
- the addition of glass can be accomplished by adding SiH 4 to the plasma gas along with a correct proportion of oxygen.
- the overall system 100 of the invention is depicted in Figure 3.
- An RF generator and an impedance-matching network are used in the system.
- the RF generator and the matching network include a primary power unit capable in this example of producing more than 5000 watts of output at 13.56 MHz, an impedance matching network that consists of a coil and two large tuning capacitors, along with a controller to set the capacitor and monitor the power reflected from the induction zone.
- the configuration of the coils and chamber are described below.
- the range of gas flow rates necessary to achieve a stable plasma are also described below.
- a commercial plasma generator developed for use as a low-pressure etching system for use in the semiconductor industry was modified to produce reactive atoms in a flowing argon stream.
- the plasma chamber 102 containing the torch and load coils (Fig. 4) was built from copper and attached directly to the impedance-matching network.
- a four-turn coil is used to couple energy into the discharge, although the exact configuration of the coil cane be altered and the number of turns either increased or decreased to help minimize reflected power and to keep the tuning requirements of the circuit within the range of the impedance matching network..
- the energy from the RF generator was shunted directly through the water-cooled coil, constructed from 3- mm copper tubing. Unless the plasma is ignited, there is very little resistance to the energy flow. The 5 kW from the generator either (1) reflects back to the source, or (2) flows to ground. After ignition, the power is inductively coupled into the plasma, and very little power is either reflected or lost to ground.
- the discharge occurs in the region of the coils.
- a crossed X-Y slide and a rotary stage allow the fabrication of rotationally symmetric workpiece up to 200 mm in diameter. Repositioning both the torch and the sample mount within the respective chamber can increase the range of the stages. In the initial system, the stages have a translation distance of 6".
- a large ventilation duct removes reaction products and the host argon gas along with any unreacted chemicals from the sample chamber.
- the first gas used to generate fluorine atoms was a mixture of sulfur hexafluoride (SF 6 ) in a nitrogen matrix.
- the nitrogen seemed to promote quenching of the reactive atoms, lowering the etch rate to nearly zero and complicating plasma tuning.
- the precursor was switched to pure SF 6 reducing quenching and improving tuning sensitivity.
- SF 6 appeared to deposit sulfur on the surface of the plasma chamber as well as the sample box (104) and the ventilation system. Energy in the radio frequency range tends to propagate along the surface of a metal. Adding a dielectric to the surface in the form of a sulfur compound substantially altered the system tuning characteristics.
- the exterior of the plasma chamber and sample box was measured for RF leakage.
- the detection system was calibrated by placing it inside the plasma chamber without igniting the plasma. The generator was then operated over a range of power from 0.1 to 1.0 kW to estimate the sensitivity of the detector. Power levels outside the plasma chamber and sample box as well as inside the sample box over the entire range of operating conditions with and without plasma ignition were measured. Not surprisingly, radiation was detected in the workpiece area, although the energy levels were very low when the plasma was ignited. Outside the plasma chamber (102) and sample box (104), it was not possible to detect any RF signal.
- the length of the outer torch tube was increased in several steps until it nearly touched the workpiece.
- a demountable torch was used.
- the demountable system permits a change in the tube length without dismantling of the entire torch assembly.
- reaction rates at the surface of the workpiece did increase, suggesting an increase in the reactive atom population.
- surface temperatures also increased.
- Thermocouples were placed at several locations in the sample box; one above the sample, one between the sample and the rotary stage and two others at probable hot spots in the chamber.
- the maximum temperature of the workpiece (measured from the rear of a silicon wafer) increased from 70 °C with the short torch (106), to 225 °C with the longest torch (106). With a sample as thin as the silicon wafer, the maximum temperature is reached quickly, a matter of a few minutes, and stays there for the duration of the exposure. At this time, the major concern with the temperature increase is resistance of the stage and motor. To prevent overheating, the sample (114) and chuck (116) were connected to the rotary stage with a stainless steel extension. The chuck (116) and the motor were also covered with a cooling coil. [0060] A silicon wafer with a known mass was exposed to a flow of fluorine atoms from the reactive atom plasma. The fluorine atoms were created from the dissociation of
- the chemistry used in the process examples is as follows.
- the sample materials processed include: Silicon dioxide (fused quartz) where the balanced reaction of concern is:
- Si0 2 + CF 4 ⁇ SiF 4 + C02 Silicon carbide has been tested and can be etched with or without the addition 0 2 .
- the use of 0 2 greatly speeds the operation.
- the balanced equation is:
- Reactive species can be introduced to the plasma by aspirating solutions into the central channel (see below).
- an aqueous solution of HF is useful.
- the HF supplies the fluorine and the water provides oxygen, if needed.
- Preferred System 100 There are several basic blocks to the preferred system 100, each described in more detail in following paragraphs.
- the plasma box 102 was separated from the sample chamber 104, so the torch 106 could be reused with bigger workpieces or with stages 108, 110, 112 with more travel. Since system 100 is a deposition system as well, the torch is separated from the sample so that a long condensation tube can be installed. The entire system mounts on an optical table. As the removal tool is a ball of hot gas, it is not very vibration sensitive.
- the system 100 further includes the RF power supply 120, the gas supply 124 which is in the form of gas cylinders, the gas supply line 126, and the tuning capacitors 128. Further, the flow control heads 118 are depicted. These heads are described hereinbelow.
- the Plasma Box 102 functions to shield the operator from the radio frequency energy generated during the process and from lV light produced by plasma. It is kept under a slight negative pressure through a connection to a chemical hood exhaust system.
- the entire enclosure is constructed from a single sheet of copper that has been folded rather then connected from individual plates.
- One of the characteristics of RF is that it travels along a surface rather than through a metal. It tends to find and leak out of seams and around door frames. All edges cannot be avoided, so that the ones that do not move, like the edges of the box, are filled with silver solder and ground with a radius. As a result, there are no sharp point or edges in the system.
- the components that do move, doors etc., are bolted tight.
- a three tube torch is shown. These are purchased from a variety of sources.
- the torch consists of three concentric tubes.
- the outer tube handles the bulk of the plasma gas, while the inner tube is used for sample introduction.
- Energy is coupled into the discharge in an annular region inside the torch by the coils ( Figure 2).
- Figure 2 the simplest way to introduce the reactive gas (or the analyte or a material to be deposited - see Reed 1961 (16, 17)) is in the center.
- the reactive gas can be mixed with the plasma gas.
- the central channel is used. This allowed for erasing small damage zones.
- the second of the three tubes introduces the auxiliary gas typically at about 1 L/min.
- the auxiliary gas has two functions; to keep the hot plasma away from the inner tube, as even a brief contact can seal it shut, and to adjust the position of the discharge in space.
- the auxiliary channel could be eliminated if desired.
- the inner diameter of the outer tube controls the size of the discharge. On the depicted torch, this is 18 mm or so.
- torches of a two tube design as small as 6 mm id. were built. Large torches with, for example, a 100 mm opening can produce a 150 mm footprint. If more volume is needed for bulk material removal, multi-head arrangement can be used. Alternatively, a demountable system where the tubes are individually held can be used. In case of damage or a change in operating conditions, each tube can be replaced separately.
- the Sample Box 104 contains the workpiece 114, chuck 116, rotational stage 108 and translation stages 110 and 112 ( Figure 4). Construction is from aluminum plates bolted together. It is unnecessary to use copper at this stage because there is no need to shield from RF.
- the sample box 104 is connected directly to the adjoining torch box 102 through a circular hole. There is a window to watch the part during the process and several holes drilled in the early phase of the project for ventilation intake.
- the main exhaust system is connected to the top of the chamber. Other designs can have the exhaust hose or the stage in a different location to minimize turbulence around the sample.
- the main components inside the chamber with the exception of the sample are the rotational and translation stages 108, 110, 112 and the chuck 116.
- the chuck is a vacuum chuck. It is mounted to the rotary stage 108 and connected to a carbon vane pump through rotary connection.
- the chuck 1 16 preferably is smaller than or equal to the size of the workpiece. If it protrudes past the part, even though it is behind the workpiece, a small amount of chuck material can deposit on the edge or surface.
- the Control System for the Stages [0074] If any shape on the workpiece is required, other than a Gaussian hole of various depths, it is desirable to translate the part relative to the torch.
- the translation speed across the workpiece can preferably be controlled in a stepwise fashion (i.e. traverse a certain distance at a fixed speed and at a certain point change the speed).
- Mass Flow Controllers 118 ( Figure 4)
- Both rotometers and mass flow controllers 118 for metering gas flow can be used.
- the system uses mass flow controllers with piezoelectric transducers to monitor gas flow on all lines except the auxiliary. These are commercially available units calibrated for argon.
- the power source 120 and control panel 122 are rack mounted outside the clean area. This is a commercial power unit 120 primarily created for low pressure capacitively coupled discharges, but easily adapted to this purpose.
- the reactive gas is preferably carbon tetrafluoride (CF 4 ) or fluorine gas (F 2 ). It is a gas at room temperature and is usually introduced into the central channel. Most of the process development has been with CF 4 although F 2 offers a number of advantages, chiefly the absence of carbon; however, F 2 is more difficult to handle as a precursor.
- Carbon tetrafluoride is used in various concentrations from 100% CF 4 to a 1% mixture, always diluted with argon (Ar). The concentrations can also be lower than 1 %.
- the reactive gas introduction is controlled by a mass flow controller over a range of 100 ml of CF 4 per minute (in the 10% mixture which was used most of the time) to as low as 0.05 ml per minute with an accuracy in the range of +/-2%.
- a mass flow controller over a range of 100 ml of CF 4 per minute (in the 10% mixture which was used most of the time) to as low as 0.05 ml per minute with an accuracy in the range of +/-2%.
- the CF 4 can also be mixed with helium and also H 2 . Nitrogen does not work though. There appears to be a quenching effect. As a result, NF 3 would not be likely to work as effectively as CF 4 .
- the pulse introduction mode would be useful when the precursors would tend to react with each other than the workpiece.
- the main gas flow serves to supply the discharge with a flowing stream of argon.
- the flow rate can be changed over a fairly wide range, from zero to 40 L/min. If it is really going fast, the plasma can blow out.
- a large flow rate means a dilution of both the reactive gas and of the energy put into the system. Flows of between 12 L/min and 20 L/min have been used for all of the work with 15.00 L/min and 19.85 L/min being the standard settings.
- the auxiliary gas is in the 1 L/min range. Presently to conserve argon, the plasma gas is run at 15 L/min if the power is 1.75 kW or less and up to 20 L/min if the system is operated up to 2.5 kW.
- One of the features of the systems is the dynamic range of material removal.
- the reactive gas can be delivered in such minute quantities that single atomic layers are removed over a period of seconds or even minutes.
- the significance of the time is that the system can be turned on and off to remove a single atomic layer of (or on) the surface.
- CF 4 can be a major proportion of the plasma gas, possibly up to 100%. With a larger discharge and a higher gas flow rate, assuming about 30% reaction efficiency, thousands of cubic centimeters of material per hour can be removed.
- the prototype system is capable of removing 10 cubic centimeters per hour under normal operating conditions.
- Power Settings There are a wide range of power conditions under which the system can operate.
- a complete unit including a power supply, a tuning circuit, and a torch box and torch, can be purchased commercially and is used exclusively for emission spectroscopy. In that application, the only purpose is to provide excited-state atoms for observation as an analysis tool.
- the power supplies themselves are available from a great number of manufacturers and are found in any semiconductor fab typically used for reactive ion etch tools. Similar units have been used in the deposition mode for growing crystals (see Reed 1961 ).
- the RF unit 120 operates at 13.56 MHZ; however, these generators are also available to run at 27.12 MHZ.
- the RF unit has a maximum power of 5.4 kW in this example only.
- the system is usually not operated above 2.5 kW and usually runs at
- the process produces a volatile reaction product.
- the inner zones of the discharge where the precursor is fragmented into atoms is between 5,000 °C and
- the plasma is a non-equilibrium system, the technique used to measure temperature determines the number obtained.
- the lower value, 5,000 °C is a gas kinetic temperature and is believed to bear the largest responsibility for heating the part.
- the material removal reaction occurs downstream from the energetic region of the plasma and is substantially lower in temperature. Removal can occur even if the workpiece is at or near room temperature.
- the role of the plasma in this process is primarily twofold.
- the discharge serves to fragment reactive precursors and to distribute the reactive species in a uniform and predictable fashion. Thus, there is a stable distribution of reactive species.
- a secondary effect is the addition of heat to the system and the effect that has on reaction rates. Any system that can supply energy to fragment the precursor will serve in this application.
- a flame from a combustion reaction is also a plasma and will work equally well as an source for reactive species. This fact is also well documented in the analytical chemistry literature where flames were the standard atom sources for decades before the introduction of inert gas plasma sources.
- the depression left by the etching was Gaussian in shape, roughly 300 micrometers in depth with a width of 30 mm.
- Atmospheric gasses tend to cool the plasma and quench the excited state species a short distance outside the discharge zone. This, in effect, gives a short range over which the removal reactions can occur.
- the presence of atmospheric pressure air will also cool the sample.
- the sample itself may be responsible for some of the planarization effect. Energy is much more efficiently conducted away from a flat, homogeneous surface. A rough surface would have spikes that poke into the more energetic regions of the plasma. They would heat up quicker and have fewer pathways to drain away the heat build-up. A fast pass under the plasma can have the effect of planarizing a surface without heating the part.
- An application for the invention process is the planarization of vapor or sputter deposited copper surfaces. Copper is the new material for wiring in the latest generator of IC * s.
- a distribution of reactive species can be obtained that is roughly Gaussian in nature and, for a 18 mm i.d. torch, has a spread of about 30 mm (Figure 5).
- a hole was produced by a 1.5 kW plasma with a reactive gas flow rate of 50 mis/minute over a 15 minute period.
- the distance from the load coils (energy induction zone) to the part surface was 25 mm.
- the reaction time was increased or decreased, the hole got deeper or shallower, but not perceptibly wider.
- a factor in this process is that the footprint is stable and dependent on controllable parameters.
- the plasma could be used to put down a coating; however, a more useful attribute may be the ability to subtly alter the chemistry of the surface.
- a slight addition of oxygen in the plasma at the beginning of the process can clean all organic material from the surface.
- Reactive surfaces can be capped (as a prevention for corrosion) or a controlled and limited production of surface oxide can be put down as a passivation layer.
- INDUSTRIAL APPLICABILITY [0091] Industry benefits from the development of a plasma shaping process in a number of ways. As already mentioned, the production of complicated optics would be simplified and, in some cases, permit the construction of workpieces that could not be made by any other means.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002560985A JP2004518526A (en) | 2001-01-30 | 2002-01-29 | Atmospheric pressure reactive atom plasma processing apparatus and method for undamaged surface shaping |
EP02706044A EP1363859A4 (en) | 2001-01-30 | 2002-01-29 | Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US26533201P | 2001-01-30 | 2001-01-30 | |
US60/265,332 | 2001-01-30 | ||
US10/002,035 US7510664B2 (en) | 2001-01-30 | 2001-11-01 | Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces |
US10/002,035 | 2001-11-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002060828A2 true WO2002060828A2 (en) | 2002-08-08 |
WO2002060828A3 WO2002060828A3 (en) | 2002-09-19 |
Family
ID=26669824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/002507 WO2002060828A2 (en) | 2001-01-30 | 2002-01-29 | Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces |
Country Status (4)
Country | Link |
---|---|
US (1) | US7510664B2 (en) |
EP (1) | EP1363859A4 (en) |
JP (2) | JP2004518526A (en) |
WO (1) | WO2002060828A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004005206A1 (en) * | 2002-07-09 | 2004-01-15 | Heraeus Tenevo Gmbh | Method and device for producing a blank mold from synthetic quartz glass by using a plasma-assisted deposition method |
CN112639195A (en) * | 2018-09-04 | 2021-04-09 | Surfx技术有限责任公司 | Apparatus and method for plasma processing of electronic materials |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7591957B2 (en) * | 2001-01-30 | 2009-09-22 | Rapt Industries, Inc. | Method for atmospheric pressure reactive atom plasma processing for surface modification |
US6660177B2 (en) | 2001-11-07 | 2003-12-09 | Rapt Industries Inc. | Apparatus and method for reactive atom plasma processing for material deposition |
US20050103441A1 (en) * | 2001-11-14 | 2005-05-19 | Masanobu Honda | Etching method and plasma etching apparatus |
JP3814558B2 (en) * | 2002-04-22 | 2006-08-30 | スピードファム株式会社 | Local dry etching method and semiconductor wafer surface position-thickness data processing method |
US7483152B2 (en) * | 2004-03-03 | 2009-01-27 | Baker Hughes Incorporated | High resolution statistical analysis of localized corrosion by direct measurement |
US20060016459A1 (en) * | 2004-05-12 | 2006-01-26 | Mcfarlane Graham | High rate etching using high pressure F2 plasma with argon dilution |
US20060084276A1 (en) * | 2004-10-14 | 2006-04-20 | Janet Yu | Methods for surface treatment and structure formed therefrom |
ES2302668T3 (en) * | 2004-11-19 | 2009-04-01 | Vetrotech Saint-Gobain (International) Ag | PROCEDURE AND DEVICE FOR WORKING GLASS PLATES BY BANDS AND SURFACE AREAS. |
FR2887872B1 (en) * | 2005-07-01 | 2008-09-05 | Saint Gobain | PROCESS AND INSTALLATION FOR TREATING HOT GLASS SUBSTRATE WITH ATMOSPHERIC PRESSURE PLASMA |
DE102006020823B4 (en) * | 2006-05-04 | 2008-04-03 | Siltronic Ag | Process for producing a polished semiconductor wafer |
JP4893169B2 (en) * | 2006-08-31 | 2012-03-07 | セイコーエプソン株式会社 | Plasma processing apparatus and plasma processing method |
JP4237803B2 (en) * | 2007-02-16 | 2009-03-11 | 田中貴金属工業株式会社 | Direct ICP emission spectroscopy analysis of solid samples |
US8679300B2 (en) | 2009-02-04 | 2014-03-25 | Jefferson Science Associates, Llc | Integrated rig for the production of boron nitride nanotubes via the pressurized vapor-condenser method |
US9517523B2 (en) * | 2010-04-09 | 2016-12-13 | Illinois Tool Works Inc. | System and method of reducing diffusible hydrogen in weld metal |
US9764409B2 (en) | 2011-04-04 | 2017-09-19 | Illinois Tool Works Inc. | Systems and methods for using fluorine-containing gas for submerged arc welding |
US9396955B2 (en) | 2011-09-30 | 2016-07-19 | Tokyo Electron Limited | Plasma tuning rods in microwave resonator processing systems |
US9111727B2 (en) | 2011-09-30 | 2015-08-18 | Tokyo Electron Limited | Plasma tuning rods in microwave resonator plasma sources |
US9728416B2 (en) | 2011-09-30 | 2017-08-08 | Tokyo Electron Limited | Plasma tuning rods in microwave resonator plasma sources |
US8808496B2 (en) | 2011-09-30 | 2014-08-19 | Tokyo Electron Limited | Plasma tuning rods in microwave processing systems |
US20130115867A1 (en) * | 2011-11-08 | 2013-05-09 | General Electric Company | Enclosure system and method for applying coating |
US9348120B2 (en) | 2012-01-23 | 2016-05-24 | Flir Systems Trading Belgium Bvba | LWIR imaging lens, image capturing system having the same, and associated method |
US20130208353A1 (en) | 2012-01-23 | 2013-08-15 | Jeremy Huddleston | Lwir imaging lens, image capturing system having the same, and associated methods |
US20150109456A1 (en) | 2012-01-23 | 2015-04-23 | Flir Systems, Inc. | Tir imaging lens, image capturing system having the same, and associated methods |
US9821402B2 (en) | 2012-03-27 | 2017-11-21 | Illinois Tool Works Inc. | System and method for submerged arc welding |
US9314854B2 (en) | 2013-01-30 | 2016-04-19 | Lam Research Corporation | Ductile mode drilling methods for brittle components of plasma processing apparatuses |
US8893702B2 (en) | 2013-02-20 | 2014-11-25 | Lam Research Corporation | Ductile mode machining methods for hard and brittle components of plasma processing apparatuses |
US9741918B2 (en) | 2013-10-07 | 2017-08-22 | Hypres, Inc. | Method for increasing the integration level of superconducting electronics circuits, and a resulting circuit |
FR3037710B1 (en) * | 2015-06-19 | 2017-06-23 | Exelsius | ELECTRONIC CARD SURFACE ENABLING METHOD FOR IMPROVING THE ADHESION OF A PROTECTIVE LAYER SUCH AS A VARNISH OR AN ELECTRICAL, MECHANICAL OR THERMAL BINDER |
US11243192B2 (en) | 2016-09-27 | 2022-02-08 | Vaon, Llc | 3-D glass printable hand-held gas chromatograph for biomedical and environmental applications |
US11203183B2 (en) | 2016-09-27 | 2021-12-21 | Vaon, Llc | Single and multi-layer, flat glass-sensor structures |
US20180086664A1 (en) * | 2016-09-27 | 2018-03-29 | Vaon, Llc | Glass-sensor structures |
EP3586954B1 (en) * | 2018-06-22 | 2023-07-19 | Molecular Plasma Group SA | Improved method and apparatus for atmospheric pressure plasma jet coating deposition on a substrate |
ES2696227B2 (en) * | 2018-07-10 | 2019-06-12 | Centro De Investig Energeticas Medioambientales Y Tecnologicas Ciemat | INTERNAL ION SOURCE FOR LOW EROSION CYCLONES |
CN109087845B (en) * | 2018-09-25 | 2024-03-26 | 南方科技大学 | Monocrystalline material polishing device and method based on inductively coupled plasma |
CN114619296A (en) * | 2022-03-24 | 2022-06-14 | 哈尔滨理工大学 | Silicon carbide atmospheric plasma polishing equipment and polishing method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4035604A (en) | 1973-01-17 | 1977-07-12 | Rolls-Royce (1971) Limited | Methods and apparatus for finishing articles |
US4739147A (en) | 1987-01-30 | 1988-04-19 | The Dow Chemical Company | Pre-aligned demountable plasma torch |
Family Cites Families (137)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3264508A (en) | 1962-06-27 | 1966-08-02 | Lai William | Plasma torch |
BE795891A (en) | 1972-02-23 | 1973-06-18 | Electricity Council | PLASMA TORCH IMPROVEMENTS |
FR2224991A5 (en) | 1973-04-05 | 1974-10-31 | France Etat | |
BE806181A (en) | 1973-10-17 | 1974-02-15 | Soudure Autogene Elect | PROCESS FOR PRIMING A COLUMN OF PLASMA INSIDE AN ENCLOSURE AND ROD-ELECTRODE FOR THE EXECUTION OF THE SAID PROCESS |
LU71343A1 (en) | 1974-11-22 | 1976-03-17 | ||
JPS5673539A (en) | 1979-11-22 | 1981-06-18 | Toshiba Corp | Surface treating apparatus of microwave plasma |
US4306175A (en) | 1980-02-29 | 1981-12-15 | Instrumentation Laboratory Inc. | Induction plasma system |
US4431898A (en) | 1981-09-01 | 1984-02-14 | The Perkin-Elmer Corporation | Inductively coupled discharge for plasma etching and resist stripping |
US4439463A (en) | 1982-02-18 | 1984-03-27 | Atlantic Richfield Company | Plasma assisted deposition system |
US4440558A (en) * | 1982-06-14 | 1984-04-03 | International Telephone And Telegraph Corporation | Fabrication of optical preforms by axial chemical vapor deposition |
US4440556A (en) * | 1982-06-23 | 1984-04-03 | International Telephone And Telegraph Corporation | Optical fiber drawing using plasma torch |
US4431901A (en) | 1982-07-02 | 1984-02-14 | The United States Of America As Represented By The United States Department Of Energy | Induction plasma tube |
US4689467A (en) | 1982-12-17 | 1987-08-25 | Inoue-Japax Research Incorporated | Laser machining apparatus |
JPS59159167A (en) | 1983-03-01 | 1984-09-08 | Zenko Hirose | Manufacture of amorphous silicon film |
US4668366A (en) | 1984-08-02 | 1987-05-26 | The Perkin-Elmer Corporation | Optical figuring by plasma assisted chemical transport and etching apparatus therefor |
US4863501A (en) * | 1985-09-26 | 1989-09-05 | Polaroid Corporation, Patent Department | Method of employing plasma for finishing start rods |
JPH0651909B2 (en) | 1985-12-28 | 1994-07-06 | キヤノン株式会社 | Method of forming thin film multilayer structure |
US4674683A (en) | 1986-05-06 | 1987-06-23 | The Perkin-Elmer Corporation | Plasma flame spray gun method and apparatus with adjustable ratio of radial and tangential plasma gas flow |
US4897282A (en) | 1986-09-08 | 1990-01-30 | Iowa State University Reserach Foundation, Inc. | Thin film coating process using an inductively coupled plasma |
FR2614751B1 (en) * | 1987-04-29 | 1991-10-04 | Aerospatiale | METHOD AND DEVICE FOR THE INJECTION OF A MATERIAL IN A FLUID FORM INTO A HOT GAS FLOW AND APPARATUS USING THE SAME |
FR2616614B1 (en) | 1987-06-10 | 1989-10-20 | Air Liquide | MICROWAVE PLASMA TORCH, DEVICE COMPRISING SUCH A TORCH AND METHOD FOR MANUFACTURING POWDER USING THE SAME |
JPH0615415B2 (en) * | 1987-10-09 | 1994-03-02 | 株式会社フジクラ | Surface treatment method for optical fiber preform |
US5007771A (en) | 1988-02-01 | 1991-04-16 | Keystone Environmental Resources, Inc. | Method for treating contaminated soil by biological degradation on a sloped surface |
JP2805009B2 (en) | 1988-05-11 | 1998-09-30 | 株式会社日立製作所 | Plasma generator and plasma element analyzer |
US5356674A (en) * | 1989-05-04 | 1994-10-18 | Deutsche Forschungsanstalt Fuer Luft-Raumfahrt E.V. | Process for applying ceramic coatings using a plasma jet carrying a free form non-metallic element |
US5106827A (en) | 1989-09-18 | 1992-04-21 | The Perkin Elmer Corporation | Plasma assisted oxidation of perovskites for forming high temperature superconductors using inductively coupled discharges |
US6068784A (en) | 1989-10-03 | 2000-05-30 | Applied Materials, Inc. | Process used in an RF coupled plasma reactor |
US5000771A (en) | 1989-12-29 | 1991-03-19 | At&T Bell Laboratories | Method for manufacturing an article comprising a refractory dielectric body |
CA2037660C (en) | 1990-03-07 | 1997-08-19 | Tadashi Kamimura | Methods of modifying surface qualities of metallic articles and apparatuses therefor |
US5256205A (en) | 1990-05-09 | 1993-10-26 | Jet Process Corporation | Microwave plasma assisted supersonic gas jet deposition of thin film materials |
US5095189A (en) * | 1990-09-26 | 1992-03-10 | General Electric Company | Method for reducing plasma constriction by intermediate injection of hydrogen in RF plasma gun |
US5629054A (en) | 1990-11-20 | 1997-05-13 | Canon Kabushiki Kaisha | Method for continuously forming a functional deposit film of large area by micro-wave plasma CVD method |
US5144151A (en) | 1991-03-20 | 1992-09-01 | Thorne Brent A | Apparatus and method for detecting the presence of a discontinuity on a glass surface |
US5200595A (en) | 1991-04-12 | 1993-04-06 | Universite De Sherbrooke | High performance induction plasma torch with a water-cooled ceramic confinement tube |
US5254830A (en) | 1991-05-07 | 1993-10-19 | Hughes Aircraft Company | System for removing material from semiconductor wafers using a contained plasma |
RU2030811C1 (en) | 1991-05-24 | 1995-03-10 | Инженерный центр "Плазмодинамика" | Solid body plasma processing plant |
US5820940A (en) | 1991-09-05 | 1998-10-13 | Technalum Research, Inc. | Preparation of adhesive coatings from thermally reactive binary and multicomponent powders |
US5349154A (en) | 1991-10-16 | 1994-09-20 | Rockwell International Corporation | Diamond growth by microwave generated plasma flame |
JPH0782918B2 (en) * | 1991-11-11 | 1995-09-06 | 株式会社三社電機製作所 | Induction plasma torch |
US5290382A (en) | 1991-12-13 | 1994-03-01 | Hughes Aircraft Company | Methods and apparatus for generating a plasma for "downstream" rapid shaping of surfaces of substrates and films |
US5336355A (en) | 1991-12-13 | 1994-08-09 | Hughes Aircraft Company | Methods and apparatus for confinement of a plasma etch region for precision shaping of surfaces of substances and films |
US5291415A (en) | 1991-12-13 | 1994-03-01 | Hughes Aircraft Company | Method to determine tool paths for thinning and correcting errors in thickness profiles of films |
US5206471A (en) * | 1991-12-26 | 1993-04-27 | Applied Science And Technology, Inc. | Microwave activated gas generator |
US5280154A (en) | 1992-01-30 | 1994-01-18 | International Business Machines Corporation | Radio frequency induction plasma processing system utilizing a uniform field coil |
US5302237A (en) | 1992-02-13 | 1994-04-12 | The United States Of America As Represented By The Secretary Of Commerce | Localized plasma processing |
US5238532A (en) | 1992-02-27 | 1993-08-24 | Hughes Aircraft Company | Method and apparatus for removal of subsurface damage in semiconductor materials by plasma etching |
US5376224A (en) | 1992-02-27 | 1994-12-27 | Hughes Aircraft Company | Method and apparatus for non-contact plasma polishing and smoothing of uniformly thinned substrates |
US5292400A (en) | 1992-03-23 | 1994-03-08 | Hughes Aircraft Company | Method and apparatus for producing variable spatial frequency control in plasma assisted chemical etching |
US5680382A (en) | 1992-04-10 | 1997-10-21 | Canon Kabushiki Kaisha | Optical information recording apparatus and method capable of handling a plurality of card-like recording media of different reflectance |
US5364434A (en) | 1992-09-30 | 1994-11-15 | The United States Of America As Represented By The Secretary Of The Navy | Plasma treatment of glass surfaces to remove carbon |
EP0595159B1 (en) | 1992-10-26 | 1997-12-29 | Schott Glaswerke | Process and apparatus for interior coating of strongly curved, essentially dome-shaped substrates by CVD |
US5429730A (en) | 1992-11-02 | 1995-07-04 | Kabushiki Kaisha Toshiba | Method of repairing defect of structure |
US5346578A (en) | 1992-11-04 | 1994-09-13 | Novellus Systems, Inc. | Induction plasma source |
US5298714A (en) * | 1992-12-01 | 1994-03-29 | Hydro-Quebec | Plasma torch for the treatment of gases and/or particles and for the deposition of particles onto a substrate |
US5386119A (en) | 1993-03-25 | 1995-01-31 | Hughes Aircraft Company | Apparatus and method for thick wafer measurement |
US5372674A (en) | 1993-05-14 | 1994-12-13 | Hughes Aircraft Company | Electrode for use in a plasma assisted chemical etching process |
US5344524A (en) | 1993-06-30 | 1994-09-06 | Honeywell Inc. | SOI substrate fabrication |
US5298103A (en) | 1993-07-15 | 1994-03-29 | Hughes Aircraft Company | Electrode assembly useful in confined plasma assisted chemical etching |
US5430355A (en) | 1993-07-30 | 1995-07-04 | Texas Instruments Incorporated | RF induction plasma source for plasma processing |
US5364496A (en) | 1993-08-20 | 1994-11-15 | Hughes Aircraft Company | Highly durable noncontaminating surround materials for plasma etching |
US5419803A (en) | 1993-11-17 | 1995-05-30 | Hughes Aircraft Company | Method of planarizing microstructures |
US5375064A (en) | 1993-12-02 | 1994-12-20 | Hughes Aircraft Company | Method and apparatus for moving a material removal tool with low tool accelerations |
FR2722939B1 (en) | 1994-07-22 | 1996-08-23 | Alcatel Fibres Optiques | INDUCTION PLASMA TORCH |
US5563709A (en) | 1994-09-13 | 1996-10-08 | Integrated Process Equipment Corp. | Apparatus for measuring, thinning and flattening silicon structures |
US5811022A (en) | 1994-11-15 | 1998-09-22 | Mattson Technology, Inc. | Inductive plasma reactor |
US5468955A (en) | 1994-12-20 | 1995-11-21 | International Business Machines Corporation | Neutral beam apparatus for in-situ production of reactants and kinetic energy transfer |
US5811021A (en) | 1995-02-28 | 1998-09-22 | Hughes Electronics Corporation | Plasma assisted chemical transport method and apparatus |
US5591068A (en) | 1995-03-13 | 1997-01-07 | Regents Of The University Of California | Precision non-contact polishing tool |
US6821500B2 (en) * | 1995-03-14 | 2004-11-23 | Bechtel Bwxt Idaho, Llc | Thermal synthesis apparatus and process |
US5795493A (en) | 1995-05-01 | 1998-08-18 | Motorola, Inc. | Laser assisted plasma chemical etching method |
US5688415A (en) | 1995-05-30 | 1997-11-18 | Ipec Precision, Inc. | Localized plasma assisted chemical etching through a mask |
US5650032A (en) | 1995-06-06 | 1997-07-22 | International Business Machines Corporation | Apparatus for producing an inductive plasma for plasma processes |
US6288225B1 (en) * | 1996-05-09 | 2001-09-11 | Pfizer Inc | Substituted benzolactam compounds as substance P antagonists |
JP3877082B2 (en) * | 1995-08-10 | 2007-02-07 | 東京エレクトロン株式会社 | Polishing apparatus and polishing method |
JPH0964321A (en) | 1995-08-24 | 1997-03-07 | Komatsu Electron Metals Co Ltd | Manufacture of soi substrate |
US5965034A (en) | 1995-12-04 | 1999-10-12 | Mc Electronics Co., Ltd. | High frequency plasma process wherein the plasma is executed by an inductive structure in which the phase and anti-phase portion of the capacitive currents between the inductive structure and the plasma are balanced |
US6017221A (en) | 1995-12-04 | 2000-01-25 | Flamm; Daniel L. | Process depending on plasma discharges sustained by inductive coupling |
US5683548A (en) | 1996-02-22 | 1997-11-04 | Motorola, Inc. | Inductively coupled plasma reactor and process |
JPH09252100A (en) | 1996-03-18 | 1997-09-22 | Shin Etsu Handotai Co Ltd | Manufacture of bonded wafer and the wafer manufactured by the method |
JPH09251935A (en) | 1996-03-18 | 1997-09-22 | Applied Materials Inc | Plasma igniter, semiconductor producing apparatus using plasma and plasma igniting method for semiconductor device |
JP3620554B2 (en) | 1996-03-25 | 2005-02-16 | 信越半導体株式会社 | Semiconductor wafer manufacturing method |
JP3252702B2 (en) | 1996-03-28 | 2002-02-04 | 信越半導体株式会社 | Method for manufacturing semiconductor single crystal mirror-finished wafer including vapor phase etching step and semiconductor single crystal mirror wafer manufactured by this method |
US5932293A (en) | 1996-03-29 | 1999-08-03 | Metalspray U.S.A., Inc. | Thermal spray systems |
US5928527A (en) * | 1996-04-15 | 1999-07-27 | The Boeing Company | Surface modification using an atmospheric pressure glow discharge plasma source |
DE69706983T2 (en) | 1996-05-31 | 2002-05-29 | Ipec Prec Inc N D Ges D Staate | SYSTEM FOR TREATING SUBSTRATES WITH A PLASMA JET |
WO1997046056A1 (en) | 1996-05-31 | 1997-12-04 | Ipec Precision, Inc. | Apparatus for generating and deflecting a plasma jet |
US6170428B1 (en) | 1996-07-15 | 2001-01-09 | Applied Materials, Inc. | Symmetric tunable inductively coupled HDP-CVD reactor |
US5897712A (en) | 1996-07-16 | 1999-04-27 | Applied Materials, Inc. | Plasma uniformity control for an inductive plasma source |
US6056848A (en) | 1996-09-11 | 2000-05-02 | Ctp, Inc. | Thin film electrostatic shield for inductive plasma processing |
US6312554B1 (en) * | 1996-12-05 | 2001-11-06 | Applied Materials, Inc. | Apparatus and method for controlling the ratio of reactive to non-reactive ions in a semiconductor wafer processing chamber |
US5767627A (en) | 1997-01-09 | 1998-06-16 | Trusi Technologies, Llc | Plasma generation and plasma processing of materials |
US5955383A (en) | 1997-01-22 | 1999-09-21 | Taiwan Semiconductor Manufacturing Company Ltd. | Method for controlling etch rate when using consumable electrodes during plasma etching |
US5961772A (en) | 1997-01-23 | 1999-10-05 | The Regents Of The University Of California | Atmospheric-pressure plasma jet |
US5800621A (en) | 1997-02-10 | 1998-09-01 | Applied Materials, Inc. | Plasma source for HDP-CVD chamber |
JP3917703B2 (en) * | 1997-02-18 | 2007-05-23 | スピードファム株式会社 | Plasma etching method and apparatus |
DE19713352A1 (en) | 1997-03-29 | 1998-10-01 | Deutsch Zentr Luft & Raumfahrt | Plasma torch system |
JP3333110B2 (en) * | 1997-04-23 | 2002-10-07 | 積水化学工業株式会社 | Surface treatment method using discharge plasma |
FR2764163B1 (en) * | 1997-05-30 | 1999-08-13 | Centre Nat Rech Scient | INDUCTIVE PLASMA TORCH WITH REAGENT INJECTOR |
US5877471A (en) | 1997-06-11 | 1999-03-02 | The Regents Of The University Of California | Plasma torch having a cooled shield assembly |
US6482476B1 (en) * | 1997-10-06 | 2002-11-19 | Shengzhong Frank Liu | Low temperature plasma enhanced CVD ceramic coating process for metal, alloy and ceramic materials |
US5925266A (en) * | 1997-10-15 | 1999-07-20 | The Perkin-Elmer Corporation | Mounting apparatus for induction coupled plasma torch |
US6194036B1 (en) | 1997-10-20 | 2001-02-27 | The Regents Of The University Of California | Deposition of coatings using an atmospheric pressure plasma jet |
US6139678A (en) | 1997-11-20 | 2000-10-31 | Trusi Technologies, Llc | Plasma processing methods and apparatus |
US6148764A (en) | 1997-12-29 | 2000-11-21 | Jet Process Corporation | Multiple micro inlet silane injection system for the jet vapor deposition of silicon nitride with a microwave discharge jet source |
US6093655A (en) | 1998-02-12 | 2000-07-25 | Micron Technology, Inc. | Plasma etching methods |
US6230719B1 (en) * | 1998-02-27 | 2001-05-15 | Micron Technology, Inc. | Apparatus for removing contaminants on electronic devices |
US6085688A (en) | 1998-03-27 | 2000-07-11 | Applied Materials, Inc. | Method and apparatus for improving processing and reducing charge damage in an inductively coupled plasma reactor |
JPH11345801A (en) * | 1998-05-29 | 1999-12-14 | Shibaura Mechatronics Corp | Vacuum processing apparatus |
US6074947A (en) | 1998-07-10 | 2000-06-13 | Plasma Sil, Llc | Process for improving uniform thickness of semiconductor substrates using plasma assisted chemical etching |
US6041623A (en) | 1998-08-27 | 2000-03-28 | Lucent Technologies Inc. | Process for fabricating article comprising refractory dielectric body |
US6406590B1 (en) * | 1998-09-08 | 2002-06-18 | Sharp Kaubushiki Kaisha | Method and apparatus for surface treatment using plasma |
JP2000096247A (en) * | 1998-09-22 | 2000-04-04 | Komatsu Ltd | Surface treating device |
KR100277833B1 (en) | 1998-10-09 | 2001-01-15 | 정선종 | Radio Wave Induced Plasma Source Generator |
EP0997926B1 (en) * | 1998-10-26 | 2006-01-04 | Matsushita Electric Works, Ltd. | Plasma treatment apparatus and method |
JP3814431B2 (en) * | 1998-12-03 | 2006-08-30 | 松下電器産業株式会社 | Manufacturing method of semiconductor device |
JP2000183044A (en) * | 1998-12-11 | 2000-06-30 | Chemitoronics Co Ltd | Plasma etching device and method |
US6028286A (en) | 1998-12-30 | 2000-02-22 | Lam Research Corporation | Method for igniting a plasma inside a plasma processing reactor |
JP4169854B2 (en) * | 1999-02-12 | 2008-10-22 | スピードファム株式会社 | Wafer planarization method |
US6153852A (en) | 1999-02-12 | 2000-11-28 | Thermal Conversion Corp | Use of a chemically reactive plasma for thermal-chemical processes |
JP2000257826A (en) * | 1999-03-02 | 2000-09-22 | Toshiba Corp | Method and device for plasma treatment |
US6262523B1 (en) * | 1999-04-21 | 2001-07-17 | The Regents Of The University Of California | Large area atmospheric-pressure plasma jet |
JP3408994B2 (en) * | 1999-05-24 | 2003-05-19 | 株式会社日立製作所 | Plasma processing apparatus and control method for plasma processing apparatus |
DE19925790A1 (en) * | 1999-06-05 | 2000-12-07 | Inst Oberflaechenmodifizierung | High rate processing of material surfaces especially in optical applications, microelectronics or in microsystems comprises using a plasma beam source |
US6200908B1 (en) | 1999-08-04 | 2001-03-13 | Memc Electronic Materials, Inc. | Process for reducing waviness in semiconductor wafers |
US6229111B1 (en) * | 1999-10-13 | 2001-05-08 | The University Of Tennessee Research Corporation | Method for laser/plasma surface alloying |
US6203661B1 (en) | 1999-12-07 | 2001-03-20 | Trusi Technologies, Llc | Brim and gas escape for non-contact wafer holder |
KR100499118B1 (en) * | 2000-02-24 | 2005-07-04 | 삼성전자주식회사 | Monolithic fluidic nozzle assembly using mono-crystalline silicon wafer and method for manufacturing the same |
US6468833B2 (en) * | 2000-03-31 | 2002-10-22 | American Air Liquide, Inc. | Systems and methods for application of substantially dry atmospheric plasma surface treatment to various electronic component packaging and assembly methods |
AUPQ861500A0 (en) * | 2000-07-06 | 2000-08-03 | Varian Australia Pty Ltd | Plasma source for spectrometry |
US6491978B1 (en) * | 2000-07-10 | 2002-12-10 | Applied Materials, Inc. | Deposition of CVD layers for copper metallization using novel metal organic chemical vapor deposition (MOCVD) precursors |
JP2002237480A (en) * | 2000-07-28 | 2002-08-23 | Sekisui Chem Co Ltd | Method of treating base material with discharge plasma |
US6929865B2 (en) * | 2000-10-24 | 2005-08-16 | James J. Myrick | Steel reinforced concrete systems |
US6534921B1 (en) * | 2000-11-09 | 2003-03-18 | Samsung Electronics Co., Ltd. | Method for removing residual metal-containing polymer material and ion implanted photoresist in atmospheric downstream plasma jet system |
US7591957B2 (en) * | 2001-01-30 | 2009-09-22 | Rapt Industries, Inc. | Method for atmospheric pressure reactive atom plasma processing for surface modification |
US6660177B2 (en) * | 2001-11-07 | 2003-12-09 | Rapt Industries Inc. | Apparatus and method for reactive atom plasma processing for material deposition |
US7304263B2 (en) * | 2003-08-14 | 2007-12-04 | Rapt Industries, Inc. | Systems and methods utilizing an aperture with a reactive atom plasma torch |
US7297892B2 (en) * | 2003-08-14 | 2007-11-20 | Rapt Industries, Inc. | Systems and methods for laser-assisted plasma processing |
-
2001
- 2001-11-01 US US10/002,035 patent/US7510664B2/en not_active Expired - Fee Related
-
2002
- 2002-01-29 WO PCT/US2002/002507 patent/WO2002060828A2/en active Application Filing
- 2002-01-29 JP JP2002560985A patent/JP2004518526A/en active Pending
- 2002-01-29 EP EP02706044A patent/EP1363859A4/en not_active Withdrawn
-
2010
- 2010-01-18 JP JP2010008221A patent/JP2010147028A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4035604A (en) | 1973-01-17 | 1977-07-12 | Rolls-Royce (1971) Limited | Methods and apparatus for finishing articles |
US4739147A (en) | 1987-01-30 | 1988-04-19 | The Dow Chemical Company | Pre-aligned demountable plasma torch |
Non-Patent Citations (2)
Title |
---|
C. B. ZAROWIN: "Rapid, non-contact, damage-free shaping of optical & other surfaces with plasma assisted chemical etching", PROCEEDINGS OF THE 43RD ANNUAL FREQUENCY CONTROL SYMPOSIUM HELD IN DENVER, 31 May 1989 (1989-05-31), pages 623 - 626 |
See also references of EP1363859A4 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004005206A1 (en) * | 2002-07-09 | 2004-01-15 | Heraeus Tenevo Gmbh | Method and device for producing a blank mold from synthetic quartz glass by using a plasma-assisted deposition method |
US8336337B2 (en) | 2002-07-09 | 2012-12-25 | Heraeus Quarzglas Gmbh & Co. Kg | Method and device for producing a blank mold from synthetic quartz glass by using a plasma-assisted deposition method |
CN112639195A (en) * | 2018-09-04 | 2021-04-09 | Surfx技术有限责任公司 | Apparatus and method for plasma processing of electronic materials |
EP3847301A4 (en) * | 2018-09-04 | 2022-05-04 | Surfx Technologies LLC | Device and method for plasma treatment of electronic materials |
Also Published As
Publication number | Publication date |
---|---|
JP2004518526A (en) | 2004-06-24 |
EP1363859A1 (en) | 2003-11-26 |
JP2010147028A (en) | 2010-07-01 |
US7510664B2 (en) | 2009-03-31 |
WO2002060828A3 (en) | 2002-09-19 |
US20020148560A1 (en) | 2002-10-17 |
EP1363859A4 (en) | 2008-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7510664B2 (en) | Apparatus and method for atmospheric pressure reactive atom plasma processing for shaping of damage free surfaces | |
US6660177B2 (en) | Apparatus and method for reactive atom plasma processing for material deposition | |
US7591957B2 (en) | Method for atmospheric pressure reactive atom plasma processing for surface modification | |
CN100406197C (en) | Normal atmosphere plasma burnishing device | |
US20050184034A1 (en) | Method for using a microwave source for reactive atom-plasma processing | |
Arnold et al. | Plasma Jet Machining: A novel technology for precision machining of optical elements | |
Fang et al. | An efficient approach for atomic-scale polishing of single-crystal silicon via plasma-based atom-selective etching | |
Li et al. | Plasma-based isotropic etching polishing of synthetic quartz | |
US9340871B1 (en) | Quality multi-spectral zinc sulfide | |
Schindler et al. | Precision optical asphere fabrication by plasma jet chemical etching (PJCE) and ion beam figuring | |
CN101265580A (en) | Pre-conditioning a sputtering target prior to sputtering | |
Li et al. | Atmospheric pressure plasma processing of fused silica in different discharge modes | |
Yadav et al. | Experimental investigations through modeling and optimization for fabrication of fused silica in medium-pressure plasma process | |
Tovstopyat et al. | Modification of the surface properties of glass-ceramic materials at low-pressure RF plasma stream | |
Jin et al. | Effect on surface roughness of zerodur material in atmospheric pressure plasma jet processing | |
Yadav et al. | Design and development of medium-pressure plasma process for optical substrate finishing: A comparative study with wet chemical etching | |
RU2141005C1 (en) | Method and device for reducing of surface roughness | |
Zhang et al. | The design of an atmospheric pressure plasma torch used for polishing ultra-smooth surfaces | |
Song et al. | Removal function and chemical composition of RS-SiC surface processing by atmospheric pressure plasma processing | |
Böhm et al. | Atmospheric plasma jet machining of optical surfaces | |
Liang et al. | Smoothing of fused silica with less damage by a hybrid plasma process combining isotropic etching and atom-migration | |
Butov et al. | Changes in the level of nitric oxide blood at patients with pulmonary multi-drug resistant tuberculosis in the process of chemotherapy | |
Yamamura et al. | Ultraprecision Finishing Process for Improving Thickness Distribution of Quartz Crystal Wafer by Utilizing Atmospheric Pressure Plasma | |
Jin et al. | Research on removal characteristic of the optical quartz with atmospheric pressure plasma jet |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002560985 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002706044 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2002706044 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |