EP1888822A1 - Melange de dopage pour le dopage de semi-conducteurs - Google Patents
Melange de dopage pour le dopage de semi-conducteursInfo
- Publication number
- EP1888822A1 EP1888822A1 EP06754014A EP06754014A EP1888822A1 EP 1888822 A1 EP1888822 A1 EP 1888822A1 EP 06754014 A EP06754014 A EP 06754014A EP 06754014 A EP06754014 A EP 06754014A EP 1888822 A1 EP1888822 A1 EP 1888822A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- doping
- mixture according
- surfactants
- dopant
- alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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Classifications
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
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- C—CHEMISTRY; METALLURGY
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
- C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
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- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/228—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a liquid phase, e.g. alloy diffusion processes
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- H—ELECTRICITY
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- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/26—Bombardment with radiation
- H01L21/263—Bombardment with radiation with high-energy radiation
- H01L21/265—Bombardment with radiation with high-energy radiation producing ion implantation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table
- H01L29/167—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic Table further characterised by the doping material
Definitions
- the invention relates to a doping mixture for the coating of semiconductor substrates, which are then fed to a high-temperature treatment for biiming a doped layer.
- the invention further relates to a method for producing such a doping mixture and its use.
- the conductivity of semiconductors is increased by incorporating foreign atoms with a slightly higher or lower valency than the semiconductor material into its crystal structure.
- this method can be applied to all types of semiconductors, but it has become particularly important in the field of doping of silicon-based semiconductors. If, for example, pentavalent phosphorus is introduced into a crystal lattice of silicon atoms, the phosphorus atom occupies a place in the crystal lattice instead of a silicon atom. Since phosphorus has five valence electrons and only four are required for bonding with its four adjacent silicon atoms, an electron with no fixed bond remains. This electron is available without energy consumption for the power line.
- Such a doped material is called n-doped and are n-type. Accordingly, insertion of an atom of lower valence than that of the semiconductor results in an electron deficit, which also leads to an increase in conductivity.
- Such materials are called p-doped and are p-type.
- In-line diffusion has many advantages over the more widely used traditional POCl 3 methods commonly used in the prior art.
- POC I 3 is usually applied in a suitable preparation as a layer on the wafer and then thermally treated in a quartz tube furnace.
- the in-line method has a large number of advantages. The wafer is relocated less frequently, resulting in a reduced risk of wafer breakage.
- the in-line method has hitherto had several disadvantages which make it difficult to exploit the efficiency which this method can offer.
- An important step for the efficiency of a doping process is on behalf of the doping source on the semiconductor to be doped.
- Some methods for applying the semiconductor with a corresponding dopant are already used, for example, in the context of the microelectronics microelectronics industry. Examples of such processes are chemical vapor deposition (CVD), in which, for example, gaseous phosphorus (for example phosphine or phosphine) is vapor-deposited on a surface to be doped.
- CVD chemical vapor deposition
- a sol-gel a solution containing or containing phosphosilicate polymer molecules dissolved or suspended in an organic solvent
- a sol-gel a solution containing or containing phosphosilicate polymer molecules dissolved or suspended in an organic solvent
- dopant on semiconductor surfaces include, for example, dipping the wafer in a dopant solution, wherein the wafers are deposited, for example, on a corresponding conveyor belt which passes through a corresponding dopant solution. It is also possible to roll up a paste or liquid containing the corresponding dopant with a roller that comes in contact with the wafer with light pressure. Both methods have in common that forming a reproducible thin and uniform layer of the dopant on the surface is associated with extremely great difficulties.
- EP 1 414 082 A2 discloses the use of aqueous solutions with doping surfactants for doping organic and inorganic semiconductors.
- a further object of the invention is to provide a doping mixture which is homogeneously distributed on a semiconductor surface, enables a homogeneous concentration of the dopant over the semiconductor surface, which is easy to apply, for example by spray application, and with the least possible economic outlay can be carried out.
- the objects underlying the invention are achieved by a doping mixture, a method for producing such a doping mixture, a method for doping semiconductors and the use of a doping mixture, as described in the following text.
- the present invention therefore provides a dopant mixture for semiconductor doping, comprising at least one p- or n-type dopant for doping a semiconductor surface, water and a mixture of two or more surfactants, wherein at least one of the surfactants is a nonionic surfactant.
- a doping mixture according to the invention contains as dopant at least one compound which is capable of forming a p- or n-doped semiconductor surface upon appropriate thermal treatment.
- derivatives of phosphorus arsenic and antimony which are suitable in the context of a doping mixture according to the invention in an appropriate form for application to a semiconductor surface are suitable as dopants in order to achieve n-doping in silicon.
- suitable derivatives of boron, aluminum, gallium or indium are suitable for forming a small p-doping.
- a dopant mixture according to the invention contains as dopant a phosphorus source, an arsenic source or an antimony source.
- a dopant mixture according to the invention contains a phosphorus source as dopant.
- Dopants which can be used in the context of the present invention should be such that, on the one hand, they are sufficiently soluble in a doping mixture according to the invention that they can be applied as homogeneously as possible to the semiconductor surface, and, on the other hand, should the corresponding dopants be such that no premature disadvantageous effect Reaction with an ingredient of the doping mixture is carried out in a manner which has adverse effects for the doping process.
- a dopant source is used which has at least one sufficiently high polarity to be soluble in a mixture of at least 10% by weight of water and optionally a further water-miscible solvent.
- a dopant source which has a solubility in water at 23 0 C of at least 0.5 g / l, for example at least 1 g / l or 5 g / l.
- a dopant mixture according to the invention contains as dopant a water-soluble phosphorus source.
- phosphoric acid or a corresponding phosphoric acid derivative for example a suitable oligophosphoric acid or polyphosphoric acid or a phosphonic acid ester, for example phosphoric acid bis (2 ethylhexyl) ester (HDEHP) or phosphoric acid mono- or dibutyl ester, or mixtures of two or more thereof, can be used as dopant.
- HDEHP phosphoric acid bis (2 ethylhexyl) ester
- phosphoric acid mono- or dibutyl ester or mixtures of two or more thereof
- a doping mixture according to the invention also contains water.
- Water is present, for example, in an amount within the scope of the doping mixture, which is sufficient to keep the doping mixture as a whole in liquid form.
- a dopant mixture according to the invention contains water in an amount which is sufficient to keep the doping mixture as a whole sprayable.
- a dopant mixture according to the invention contains a mixture of two or more surfactants, wherein at least one of the surfactants is a nonionic surfactant.
- a "mixture of two or more surfactants” is understood as meaning a surfactant mixture which has two different properties
- a surfactant mixture according to the present text can be used for example, therefore, be referred to as a mixture, because the surfactants contained in the mixture have a different chemical structure.
- a surfactant mixture contains a surfactant prepared by a polymeric construction reaction, for example, by alkoxylation
- a surfactant need not yet be referred to as a mixture because it contains oligomers of a different chain length in the range generated by the polymeric building reaction has been.
- a surfactant mixture which contains surfactants having a basic chemical structure but a different molecular weight should only be designated as a mixture if the molecular weight distribution of the surfactants in this mixture is recognizably at least bimodal.
- a bi-modality can be recognized, for example, if, by suitable measuring methods, in particular by gel permeation chromatography (GPC), light scattering or osmometry, number average molecular weights differing by at least 100, preferably by at least 200 or by at least 500 molecular weight units from one another.
- GPC gel permeation chromatography
- a doping mixture according to the invention contains at least two surfactants which differ in their chemical composition from one another.
- At least one of the surfactants used in the context of a doping mixture according to the invention is a nonionic surfactant.
- a nonionic surfactant is a compound which, although having at least a high molecular weight polarity, but no charge.
- nonionic surfactants are, for example, fatty alcohol ethoxylates, alkylphenol ethoxylates, fatty amine ethoxylates, fatty acid ethoxylates, fatty acid ester ethoxylates, other alkoxylates, alkanolamides, sugar surfactants, amine oxides and other nonionic surfactants.
- Suitable nonionic surfactants in the context of the present invention are, for example, alkyl and alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkylamides, alcohol alkoxylates, alkoxylated carboxylic acid esters, preferably alkyl and alkenyl oligoglycosides.
- Alkyl and / or alkenyl oligoglycosides are known nonionic surfactants which follow formula (1),
- R is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
- G is a sugar radical having 5 or 6 carbon atoms
- z is a number from 1 to 10.
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketones having 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
- the index number z in the general formula (1) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- alkyl and / or alkenyl oligoglycosides having a mean degree of oligomerization z of from 1.1 to 4.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and more particularly between 1.2 and 1.6 are preferred.
- the alkyl or alkenyl radical R can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
- Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis.
- alkyl or alkenyl radical R can furthermore also be derived from primary alcohols having 12 to 22, preferably 12 to 18, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 2 / i 4 -Kokos- or Palm kernel alcohol or Cu / F fatty alcohol from coconut palm kernel or palm oil with a DP of 1 to 3.
- nonionic surfactants used in the present invention either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese Patent Application JP 58/217598 Al or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 Al.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- nonionic surfactants are polyhydroxy fatty acid amides of the formula (II),
- R * for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
- [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
- R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 3 is a linear, branched or cyclic alkyl radical or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, wherein C I-4 - alkyl or phenyl groups being preferred
- [Z] is a linear polyhydroxyalkyl group, of which alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- a reducing sugar with an alkylamine or an alkanolamine
- acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- fatty acid N-alkylpolyhydroxyalkylamide is the subject of a variety of publications.
- European patent application EP 0285768 A1 discloses its use as a thickening agent.
- French laid-open specification FR 1580491 A describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and optionally soaps which contain fatty acid N-alkylglucamides as foam regulators. Mixtures of short- and long-chain glucamides are described in German Patent DE 4400632 C1 (Henkel).
- German Offenlegungsschriften DE 4326959 AI and DE 4309567 A1 also disclose the use of glucamides with longer alkyl radicals than pseudoceramides in skin care products and also by way of combinations of glucamides with protein hydrolysates and cationic surfactants in hair care products.
- WO 92/06153 A1, WO 92/06156 A1, WO 92/06157 A1, WO 92/06158 A1, WO 92/06159 A1 and WO 92/06160 A1 are mixtures of fatty acid N Alkylglucamiden with anionic surfactants, surfactants with sulfate and / or sulfonate structure, ether carboxylic acids, ether sulfates, Methylestersulfona- th and nonionic surfactants.
- alcohol ethoxylates are also usable as nonionic surfactants. These are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (IV),
- R '" is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50.
- Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and Oils or aldehydes from Roelen's oxosynthesis and as Monomerf
- alkoxylated carboxylic acid esters are also usable as nonionic surfactants.
- Such compounds are known in the art.
- such alkoxylated carboxylic acid esters are obtainable by esterification of alkoxylated carboxylic acids with alcohols.
- the compounds are prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE 3914131 A1, which provide compounds having a restricted homolog distribution.
- Both carbonic acid esters of monohydric alcohols and of polyhydric alcohols can be alkoxylated by this process.
- Preferred according to the present invention are alkoxylated carboxylic acid esters of monohydric alcohols which follow the general formula (V),
- R 4 CO is an aliphatic acyl radical derived from a carboxylic acid
- OAlk is alkylene oxide
- R 5 is an aliphatic alkyl radical derived from a monohydric aliphatic alcohol.
- Particularly suitable are alkoxylated carboxylic acid esters of the formula (V) in which R 4 CO is an aliphatic acyl radical having 6 to 30, preferably 6 to 22 and in particular 10 to 18 carbon atoms.
- n average numbers of 1 to 30, preferably 5 to 20 and in particular 10 to 15 and R 5 represents an aliphatic alkyl radical having 1 to 4 and preferably 1 and / or 2 carbon atoms.
- Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, especially linear, saturated and / or unsaturated fatty acids including technical mixtures thereof, as obtainable by lipolysis from animal and / or vegetable fats and oils, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cotton seed oil, fish oil, beef tallow and lard.
- carboxylic acids examples include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and / or erucic acid
- Preferred alkyl radicals are derived from primary, aliphatic monofunctional alcohols having 1 to 4 carbon atoms, which may be saturated and / or unsaturated.
- suitable monoalcohols examples include methanol, ethanol, propanol, and butanol, especially methanol.
- OAlk represents the alkylene oxides which are reacted with the carboxylic acid esters and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, especially ethylene oxide alone.
- the nonionic surfactants can be used in amounts of 20 to 95, preferably 50 to 80 and in particular 60 to 70 - based on the final concentration.
- hydroxymix ethers which are likewise suitable as nonionic surfactants are known nonionic surfactants having unsymmetrical ether structure and polyalkylene glycol contents, which are obtained, for example, by subjecting olefin epoxides with fatty alcohol polyglycol ethers to a ring-opening reaction.
- HME hydroxymix ethers
- Corresponding products and their use in the area of hard surface cleaning are the subject of, for example, European Patent EP 0693049 B 1 and international patent application WO 94/22800 A1 (Olive) and the publications cited therein.
- the hydroxy mixed ethers of the general formula (VI) typically follow
- R 6 is -CH (OH) -CHR 7 O (CH 2 CHR 8 O) n R 9
- R 6 is a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
- R 7 is hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
- R 8 is hydrogen or methyl
- R 9 is a linear or branched, alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and n represents numbers of 1 to 50, preferably 2 to 25 and especially 5 to 15, with the proviso that the sum of the carbon atoms in the R 6 and R 7 is at least 4 and preferably 12 to 18.
- the polar portion of the molecule may be a polyethylene glycol or a polypropylene glycol chain; Also suitable are mixed chains of PE and PP units, whether in statistical or block distribution.
- Typical examples are ring-opening products of 1,2-hexene epoxide, 2,3-hexene epoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 Decene epoxide, 4,5-decene epoxide, 1,2-dodecene epoxide, 2,3-dodecene epoxide, 3,4-dodecene epoxide, 4,5-dodecene epoxide, 5,6-dodecene epoxide, 1,2-tetradecenepoxide, 2,3-
- Caprolyl alcohol capryl alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, Erucyl alcohol and brassidyl alcohol and their technical mixtures.
- the HME are contained in the moldings in amounts of 0.1 to 20, preferably 0.5 to 8 and in particular 3 to 5 wt .-%.
- the nonionic surfactants which are particularly suitable for the purposes of the present invention are in principle capable of reducing the surface tension in an aqueous system and, in particular, of achieving a low dynamic surface tension. Dynamic surface tension is understood to mean the decrease in surface tension as a function of time.
- surfactants examples include the surfactants marketed under the name Triton, for example Triton BQ Triton CQ compounds of the Triton CF group, compounds of the Triton DF group, compounds of the Triton X series, Trition-CA, Triton N -57 or Triton X-207.
- Triton for example Triton BQ Triton CQ compounds of the Triton CF group, compounds of the Triton DF group, compounds of the Triton X series, Trition-CA, Triton N -57 or Triton X-207.
- Triton examples include Dow Chemical Corporation, Midland, Michigan.
- nonionic surfactants for example the compounds as mentioned in US 2002/0014611 A1 in paragraph [0021].
- compounds from the Triton DF series are used as nonionic surfactants, for example Triton DF-16 or Triton DF-18.
- Suitable nonionic surfactants have, for example, an HLB value of about 8 to about 14, in particular about 10 to about 13, for example about 11 to about 12.
- the pH of a 5% aqueous solution of a corresponding surfactant is preferably from about 5 to about 8, for example from about 6 to about 7.
- the equilibrium surface tension in dynes / cm is preferably from about 25 to about 36, for example from about 26 to about 35 or from about 27 to about 33 or about 28 to about 31 or about 29 to about 30.
- the dynamic surface tension in dynes / cm is about 40 to about 60, for example about 42 to about 58 or about 44 from about 56 or about 46 to about 54 or about 48 to about 52.
- the critical micelle concentration (cmc) in distilled water at 25 ° C is about 300 to about 600, for example about 350 to about 550 or about 400 to about 500 proved to be advantageous.
- Suitable nonionic surfactants preferably have a low foaming tendency and are stable in alkalis and alkaline solutions.
- a doping mixture according to the invention in the context of a preferred embodiment of the invention contains a fluorinated surfactant.
- fluorinated surfactants are for example surfactants a Q are of the general formula (R F) a (Q) t> Z wherein R f is a fluoroaliphatic radical, is 1 or 2, a linking group, and b is 1.
- R f is generally a fluorinated, preferably saturated, monovalent, non-aromatic group having at least 3 carbon atoms.
- the fluoroaliphatic radical is, for example, linearly branched or, if it has a sufficient number of carbon atoms or a sufficient size, cyclic.
- the radical R f has complete fluorination, but it is also possible that the radical still has hydrogen atoms or, for example, chlorine atoms. The latter preferably only if per 2 carbon atoms not more than 1 hydrogen atom or chlorine atom is contained in the rest.
- Particularly suitable are fluoroaliphatic radicals having from about 1 to about 12 carbon atoms.
- Q stands for a connection group which is monovalent or polyvalent.
- Q stands for an alkylene group such as methylene or ethylene, cyclohexylene, arylene or the like or for combinations of such radicals with molecular constituents which have heteroatoms, for example oxy, thio, carbonyl, Sulfonyl, sulfinyl, sulfonamido, carbonamido, ureylene, carbamato, imino and the like, and also for combinations such as sulfonamidoalkylene, carbonamidoalkyls, oxyalkylenes (eg C 2 H 4 OC 2 H 4 -), thiodialkylene (eg. C 2 H 4 SC 2 H 4 -) alkylene carbamate and the like.
- oxyalkylenes eg C 2 H 4 OC 2 H 4 -
- thiodialkylene eg. C 2 H 4 SC 2 H 4 - alkylene carba
- Z stands for a water solubility mediating polar group or such a moiety z.
- amino groups for example, NH 2 or NHR, wherein R is an alkyl radical having 1 to 4 carbon atoms, for example, methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl or tert-butyl
- sulfoammonium or carboxyammonium groups poly (oxyethylene), poly (oxypropylene), carboxylates, alkoxylates, phosphates, and the like.
- fluorinated surfactants can be used which are of formula
- R f is a perfluorinated hydrocarbon radical of the structure CF 3 - (CF 2 CF 2 ) n wherein n is from 2 to about 6.
- perfluorinated alkyl ethoxylates are commercially available, for example under the name Zonyl SFO, Zonyl SFN and Zonyl SF300 (EI DuPont).
- fluorohydrocarbon surfactants include surfactants such as Zonyl SFK, DuPont amphoteric fluorosurfactant, Zonyl SF-62 anionic fluorosurfactant from DuPont, FLURAD FC 170 non-ionic fluorosurfactant from 3M Company, or FC 123 anionic fluorosurfactant from 3M Company or L-18699A , a fluorinated surfactant of Fa 3M Company.
- a dopant mixture according to the invention contains a nonionic fluorinated surfactant.
- mixtures of the ions of ionic fluorinated surfactants preferably either mixtures of the ions of cationic fluorinated surfactants or those of anionic fluorinated surfactants.
- Anionic fluorinated surfactants comprise at least one fluorine-containing hydrophobic group and at least one negative charge carrier.
- Examples of such compounds are fluorinated carboxylic acids and their salts with inorganic or organic cations, fluorinated sulfonic acids and their salts with inorganic or organic cations, fluorinated organosulfuric acids and their salts with inorganic or organic cations, fluorinated phosphinic, phosphonic or organophosphoric acids and salts thereof with inorganic or organic cations.
- perfluorocarboxylic acids and their preferably water-soluble salts such as perfluoroalkanoic acids, for example in particular perfluoroalkanoic acids of the formula CF3 (CF-i) n -000H, where n is preferably greater than or equal to 7; partially fluorinated carboxylic acids and carboxylic acid salts, such as partially fluorinated
- Alkanoic acids partially fluorinated alkenoic acids, Perfluoralkoxyalkan Acid, Perfluoralkylethylenoxyalkan Acid, Perfluoralkoxybenzoeklaren and
- Sulfide, sulfone, carboxylic acid amide, hydroxy, oxo and / or ether groups pen- containing hydrofluorocarboxylic acids and salts thereof, for example lithium-3 - [(1H, 1H, 2H, 2H-fluoroalkyl) thio] -propionate, Zonyl FSA®, DuPont);
- Perfluorosulfonic acids and their preferably water-soluble salts such as perfluoroalkanesulfonic acids of the formula: CF 3 (CFZ) m -SO 3 H with m greater than or equal to 1;
- partially fluorinated sulfonic acids and their preferably water-soluble salts such as partially fluorinated alkanesulfonic acids, e.g. Perfluoralkylethan- sulfonic acids, Perfluorpropylethansulfonklaren, partially fluorinated alkensulfonic acids, and sulfide, Carbonklamid-, hydroxy, oxo or / and
- Ether-containing partially fluorinated sulfonic acids fluorinated sulfoesters, e.g. Sulfosuccinic acid esters, perfluoroalkylsulfopropionates, perfluoroalkylsulfobutyrates and salts thereof; e.g. Perfluoroalkylethylsulfonic acid ammonium salt, Zonyl TBS® DuP ont, sodium [tartaric acid perfluoroalkylethyl diester-2-sulfonate], Fluowet SB®,
- fluorinated sulfoesters e.g. Sulfosuccinic acid esters, perfluoroalkylsulfopropionates, perfluoroalkylsulfobutyrates and salts thereof; e.g. Perfluoroalkylethylsulfonic acid ammonium salt, Zonyl TBS® DuP ont, sodium
- Clariant GmbH fluorinated organic sulfuric acids and their salts, such as perfluoroalkylated methyl sulfates, fluorinated sulfatopoly (oxyethylene;). perfluoropropoxylated sulfates and salts thereof; fluorinated phosphinic and phosphonic acids and their preferably water-soluble salts, eg Fluowet PL80 ⁇ . Hoe S 2746. Clariant GmbH, fluorinated organic phosphoric acids and their salts, such as perfluoroalkylethylphosphoric acids. Mono- and bis- (fluoroalkyl) - (ethyl) -phosphoric acids.
- a dopant mixture according to the invention contains a non-fluorinated nonionic surfactant.
- a dopant mixture according to the invention a dopant mixture according to the invention, a nonionic non-fluorinated surfactant and a fluorinated surfactant, for example a nonionic fluorinated surfactant.
- a dopant mixture according to the invention contains the dopant, for example, in an amount of 0.01 to 80 wt .-%, for example in an amount of about 0.05 to about 60 wt .-% or about 0.1 to about 50 weight percent or about 0.5 to about 40 wt.% or about 0.8 to about 30 wt.% or about 1.0 to about 20 wt.% or about 1.2 to 15 wt.% or about 1.5 to about 10 wt .-% or about 1.8 to about 8 wt .-%.
- the percentages by weight are based on the weight of the total doping weight.
- a dopant mixture according to the invention contains a mixture of at least 2 surfactants in an amount of about 0.0011 to about 20 weight percent, for example, an amount of about 0.005 to about 15 or an amount of about 0.1 to about 10 weight percent.
- this fluorinated surfactant is present in an amount of about 0.0001 to about 5 weight percent, for example, in an amount of about 0.001 to about 2 weight percent or in an amount of about 0.01 to about 1 Percent by weight, for example, in an amount of about 0.05 to about 0.8 weight percent.
- a doping mixture according to the invention contains a non-fluorinated, nonionic surfactant, this non-fluorinated nonionic surfactant, for example from about 0.001 to about 10 weight percent, for example, from about 0.01 to about 8 weight percent, or from about 0.05 to about 6 weight percent, or from about 0.1 to about 5 weight percent or in an amount of about 0.5 to about 3 weight percent.
- this non-fluorinated nonionic surfactant for example from about 0.001 to about 10 weight percent, for example, from about 0.01 to about 8 weight percent, or from about 0.05 to about 6 weight percent, or from about 0.1 to about 5 weight percent or in an amount of about 0.5 to about 3 weight percent.
- An inventive doping mixture contains water.
- a doping mixture according to the invention may contain water in an amount which alone is insufficient to make the doping mixture in a liquid state.
- a doping mixture according to the invention contains at least one further water-miscible solvent, which as a whole provides for a liquid state of aggregation of the doping mixture at at least one temperature within a range from about 0 to about 50 ° C.
- a dopant mixture according to the invention contains at least about 10% by weight, for example at least about 20% by weight, of water.
- the proportion of water in the doping mixture according to the invention may also be significantly above said values, for example at least about 30% by weight, at least about 40% by weight, at least about 50% by weight, at least about 60% by weight , at least about 70 percent or at least about 80% by weight. In many cases it has been found to be advantageous if the proportion of water is 90% by weight or more, for example at least about 95% by weight.
- the doping mixture according to the invention is liquid at room temperature, ie for example at a temperature of about 23 ° C. It is essential in the context of the present invention that the doping mixture at the application temperature, that is, for example, at a temperature in a range of about 0 to about 100 ° C, in particular within a range of about 5 to about 50 0 C or within a range of about 10 to about 40 ° C is liquid. Preferably, the viscosity of a corresponding doping mixture is within a range that allows application by spraying.
- a doping mixture according to the invention may contain, in addition to the abovementioned compounds, one or more additives.
- suitable additives are compounds which form a solvent mixture with water.
- a suitable solvent mixture consists of water and at least one alcohol.
- any mixtures of water and one or more different alcohols can be used, provided that the remaining constituents of the doping mixture can be dissolved in a sufficient amount in the solvent mixture.
- preferred alcohols have a water solubility of at least 1 g / l, but preferably at least about 10 or at least about 30 g / l.
- Suitable alcohols have 1 to about 6 OH groups, especially about 1, 2 or 3 free OH groups, which may be primary, secondary or tertiary, but are preferably primary or secondary.
- ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, (2-methoxymethylethoxy) propanol, glycerol are particularly suitable or trimethylolpropane or mixtures of two or more of the above-mentioned alcohols.
- ether alcohols such as can be obtained by etherification of one of the abovementioned diols or triols with one of the abovementioned monoalcohols.
- Particularly suitable are the etherification products of ethylene glycol with ethanol, propanol or butanol, in particular ethylene glycol monobutyl ether (butyl glycol).
- a mixture of at least one monoalcohol and at least one ether alcohol leads to good results.
- suitable mixtures are mixtures of ethanol, n-propanol or isopropanol or a mixture of two or more thereof and ethylene glycol monobutyl ether, propylene glycol monopropyl ether or butylene glycol monoethyl ether or a mixture of two or more thereof.
- the above compounds may already be included as part of commercially available surfactants as part of the addition of such surfactant arrive in the doping mixture in the preparation of a doping mixture according to the invention.
- a dopant mixture according to the invention can be prepared in any desired manner by mixing the individual constituents.
- the present invention therefore also provides a process for producing a doping mixture according to the invention, in which at least one p- or n-dopant for doping a semiconductor surface, water and two or more surfactants, wherein at least one of the surfactants is a nonionic surfactant, are mixed ,
- a doping mixture according to the invention contains constituents which make it possible, for example, to dissolve an essential constituent of the doping mixture (for example of the dopant itself) or improve this dissolution in a manner beneficial to the use of the doping mixture according to the invention, these constituents may be present, for example, in a suitable sequence be added before the corresponding substance to be dissolved.
- a dopant mixture according to the invention may contain, for example, dopants which are not or not sufficiently soluble in water itself.
- additives such as solubilizers
- these are alcohols which improve the solubility of the corresponding dopant.
- the addition of the solubilizer can take place before or after the addition of the dopant to be dissolved.
- the solubilizer or a mixture of two or more solubilizers is used before the Addition of the substance to be dissolved, for example, before the addition of the dopant occurs.
- a dopant mixture according to the invention is suitable for doping semiconductor surfaces.
- first a semiconductor surface is subjected to a doping mixture according to the invention.
- the present invention therefore also relates to a semiconductor surface which is exposed to a doping mixture according to the invention.
- the semiconductor surface is first subjected to a doping mixture according to the invention and treated at elevated temperature in a subsequent step.
- the present invention therefore also provides a method for doping a semiconductor, in which a semiconductor surface is subjected to at least one doping mixture according to the invention and the semiconductor surface is subsequently treated at elevated temperature.
- a doping mixture according to the invention can be applied to a semiconductor surface.
- these are dipping, brushing, rolling, knife coating, spin coating printing, or applying with a sponge or a sponge-like structure, for example a roll, or spraying, for example with ultrasonic or two-fluid nozzle, and the like application method, which effetbowbar with a liquid doping mixture are.
- any spraying method by which a doping mixture according to the invention can be applied to a semiconductor surface is suitable.
- a spray device which sprays with the use of ultrasound is used to apply the doping mixture.
- Corresponding devices are known to the person skilled in the art.
- the flow rates are very low adjustable in an ultrasonic method, so that very thin dopant mixture layers can be achieved.
- the ultrasonic method is characterized in that very low drop speeds can be achieved and thus a shaping of the spray after the exit, for example by external air jets, is possible.
- a shaping of the spray after the exit for example by external air jets, is possible.
- such shaping of the spray increases the yield of the process since almost all of the sprayed substance can be accurately placed on the semiconductor surface. This minimizes the so-called overspray and improves the homogeneity of the layer.
- the application of ultrasound spraying to the semiconductor surface takes place.
- the application of the dopant mixture layer can be done on one side or, if a two-sided doping is desired, on two sides.
- the semiconductor surface can be dried, for example. This can be done for example in a continuous dryer or in a special zone of a diffusion furnace. It is also possible in the context of the present invention that the drying step is eliminated.
- the coated semiconductor surface can be thermally treated in a corresponding diffusion furnace, for example a continuous furnace or a tube furnace.
- a continuous furnace for example, the disc-shaped semiconductors are transported in a horizontal position, in a tube furnace, the semiconductors are arranged vertically, treated for example in disc carriers.
- Another object of the invention is the use of a mixture containing at least one p- or n-type dopant for doping a semiconductor surface, water and a mixture of two or more surfactants, wherein at least one of the surfactants is a nonionic surfactant, for the preparation of doped semiconductor surfaces.
- Silicon wafers were coated in an in-line unit with a mixture of 3 wt% concentrated phosphoric acid (85%), 1 wt% Triton DF-16, 0.1 wt% Zonyl FSH (50% in dipropylene glycol monomethyl ether) and Water ad 100 wt .-% coated by ultrasonic spraying.
- the flow rate of the doping mixture was about 4 ml / min at a belt speed of about 600 mm / min during spraying.
- the wafer wetted with the dopant was completely coated, including the edge regions. There were no island-like structures. After diffusion, a homogeneity of the emitter layer resistance of 2.2 ⁇ / sq.
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- Detergent Compositions (AREA)
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Abstract
L'invention concerne un mélange de dopage pour l'enduction de substrats semi-conducteurs, qui sont ensuite soumis à un traitement à haute température permettant la formation d'une couche dopée. Cette invention concerne également un procédé de production d'un mélange de dopage de ce type ainsi que son utilisation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102005025933A DE102005025933B3 (de) | 2005-06-06 | 2005-06-06 | Dotiergermisch für die Dotierung von Halbleitern |
PCT/EP2006/005195 WO2006131251A1 (fr) | 2005-06-06 | 2006-05-31 | Melange de dopage pour le dopage de semi-conducteurs |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1888822A1 true EP1888822A1 (fr) | 2008-02-20 |
Family
ID=36599650
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06754014A Withdrawn EP1888822A1 (fr) | 2005-06-06 | 2006-05-31 | Melange de dopage pour le dopage de semi-conducteurs |
Country Status (9)
Country | Link |
---|---|
US (1) | US8043946B2 (fr) |
EP (1) | EP1888822A1 (fr) |
JP (1) | JP2008543097A (fr) |
KR (1) | KR20080033934A (fr) |
AU (1) | AU2006257042B2 (fr) |
DE (1) | DE102005025933B3 (fr) |
NO (1) | NO20080047L (fr) |
TW (1) | TW200703473A (fr) |
WO (1) | WO2006131251A1 (fr) |
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AU2007220596B2 (en) * | 2006-02-28 | 2012-07-12 | Basf Se | Antimicrobial compounds |
EP2016527B1 (fr) * | 2006-05-04 | 2009-12-16 | Elektrobit Wireless Communications Ltd. | Procédé permettant de faire fonctionner un réseau RFID |
DE102007054485B4 (de) * | 2007-11-15 | 2011-12-01 | Deutsche Cell Gmbh | Siliziumoberflächen-Strukturierungs-Verfahren |
KR100835248B1 (ko) * | 2007-12-07 | 2008-06-09 | 한국열전(주) | 인산수용액을 이용한 반도체 p-n 접합층 형성 방법 및 이를 위한 인산수용액 도포장치 |
US20090239363A1 (en) * | 2008-03-24 | 2009-09-24 | Honeywell International, Inc. | Methods for forming doped regions in semiconductor substrates using non-contact printing processes and dopant-comprising inks for forming such doped regions using non-contact printing processes |
US8053867B2 (en) * | 2008-08-20 | 2011-11-08 | Honeywell International Inc. | Phosphorous-comprising dopants and methods for forming phosphorous-doped regions in semiconductor substrates using phosphorous-comprising dopants |
DE102008044485A1 (de) | 2008-08-28 | 2010-04-01 | Schott Solar Ag | Verfahren und Anordnung zum Herstellen einer Funktionsschicht auf einem Halbleiterbauelement |
US7951696B2 (en) | 2008-09-30 | 2011-05-31 | Honeywell International Inc. | Methods for simultaneously forming N-type and P-type doped regions using non-contact printing processes |
US7820532B2 (en) * | 2008-12-29 | 2010-10-26 | Honeywell International Inc. | Methods for simultaneously forming doped regions having different conductivity-determining type element profiles |
US8518170B2 (en) | 2008-12-29 | 2013-08-27 | Honeywell International Inc. | Boron-comprising inks for forming boron-doped regions in semiconductor substrates using non-contact printing processes and methods for fabricating such boron-comprising inks |
US8324089B2 (en) | 2009-07-23 | 2012-12-04 | Honeywell International Inc. | Compositions for forming doped regions in semiconductor substrates, methods for fabricating such compositions, and methods for forming doped regions using such compositions |
KR101162119B1 (ko) | 2009-10-23 | 2012-07-04 | 주식회사 효성 | 태양전지의 선택적 에미터 형성 방법 및 그 장치 |
US8691675B2 (en) * | 2009-11-25 | 2014-04-08 | International Business Machines Corporation | Vapor phase deposition processes for doping silicon |
US8858843B2 (en) * | 2010-12-14 | 2014-10-14 | Innovalight, Inc. | High fidelity doping paste and methods thereof |
US8629294B2 (en) | 2011-08-25 | 2014-01-14 | Honeywell International Inc. | Borate esters, boron-comprising dopants, and methods of fabricating boron-comprising dopants |
DE102011053085A1 (de) * | 2011-08-29 | 2013-02-28 | Schott Solar Ag | Verfahren zur Herstellung einer Solarzelle |
US8975170B2 (en) | 2011-10-24 | 2015-03-10 | Honeywell International Inc. | Dopant ink compositions for forming doped regions in semiconductor substrates, and methods for fabricating dopant ink compositions |
US9929014B2 (en) * | 2013-11-27 | 2018-03-27 | Entegris, Inc. | Dopant precursors for mono-layer doping |
US10699944B2 (en) | 2018-09-28 | 2020-06-30 | Taiwan Semiconductor Manufacturing Company, Ltd. | Surface modification layer for conductive feature formation |
JP2022519264A (ja) * | 2019-01-30 | 2022-03-22 | テグラ ソルソンィス パラ テルハドス エルティーディーエー | 光電池、カプセル化光電池の製造方法、光起電タイル用及び光起電屋根タイル用の電気接続部セット |
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-
2005
- 2005-06-06 DE DE102005025933A patent/DE102005025933B3/de not_active Expired - Fee Related
-
2006
- 2006-05-22 TW TW095118090A patent/TW200703473A/zh unknown
- 2006-05-31 JP JP2008515102A patent/JP2008543097A/ja active Pending
- 2006-05-31 WO PCT/EP2006/005195 patent/WO2006131251A1/fr active Search and Examination
- 2006-05-31 KR KR1020087000318A patent/KR20080033934A/ko not_active Application Discontinuation
- 2006-05-31 EP EP06754014A patent/EP1888822A1/fr not_active Withdrawn
- 2006-05-31 AU AU2006257042A patent/AU2006257042B2/en not_active Ceased
- 2006-05-31 US US11/916,538 patent/US8043946B2/en not_active Expired - Fee Related
-
2008
- 2008-01-03 NO NO20080047A patent/NO20080047L/no not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO2006131251A1 * |
Also Published As
Publication number | Publication date |
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KR20080033934A (ko) | 2008-04-17 |
JP2008543097A (ja) | 2008-11-27 |
US20080314288A1 (en) | 2008-12-25 |
WO2006131251A1 (fr) | 2006-12-14 |
US8043946B2 (en) | 2011-10-25 |
TW200703473A (en) | 2007-01-16 |
AU2006257042B2 (en) | 2011-07-14 |
DE102005025933B3 (de) | 2006-07-13 |
NO20080047L (no) | 2008-01-03 |
AU2006257042A1 (en) | 2006-12-14 |
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