EP1044289B1 - Plasmaborierung - Google Patents
Plasmaborierung Download PDFInfo
- Publication number
- EP1044289B1 EP1044289B1 EP98965249A EP98965249A EP1044289B1 EP 1044289 B1 EP1044289 B1 EP 1044289B1 EP 98965249 A EP98965249 A EP 98965249A EP 98965249 A EP98965249 A EP 98965249A EP 1044289 B1 EP1044289 B1 EP 1044289B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- boron
- vol
- medium
- plasma
- excited
- 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.)
- Expired - Lifetime
Links
- 238000005271 boronizing Methods 0.000 title description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 54
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims description 59
- 239000007789 gas Substances 0.000 claims description 32
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- CMIAIUZBKPLIOP-YZLZLFLDSA-N methyl (1r,4ar,4br,10ar)-7-(2-hydroperoxypropan-2-yl)-4a-methyl-2,3,4,4b,5,6,10,10a-octahydro-1h-phenanthrene-1-carboxylate Chemical compound C1=C(C(C)(C)OO)CC[C@@H]2[C@]3(C)CCC[C@@H](C(=O)OC)[C@H]3CC=C21 CMIAIUZBKPLIOP-YZLZLFLDSA-N 0.000 claims description 2
- 229910015844 BCl3 Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 10
- 238000005755 formation reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 229910052756 noble gas Inorganic materials 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 150000001638 boron Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
Definitions
- the present invention relates to a method for producing a boride layer a surface by plasma working, using a reactor Gas medium containing boron donor feeds and in the reactor Glow discharge generated.
- US 3,677,799 A describes a method for the deposition of boron on a substrate using a gas mixture of hydrogen and a boron compound.
- a pulsed high-frequency voltage is used, by means of which a first Hydrogen plasma is generated, which is then mixed with a boron compound to deposit a boron layer on the substrate.
- FR 2 708 624 A1 describes a method for plasma-assisted CVD deposition of carbon layers or silicon carbide layers described using of gas mixtures, which also contain a volume percentage of gaseous boron compounds can optionally contain. This process is primarily about deposition a carbon-containing layer on a substrate. Determining the amount of one stimulated boron medium product in the glow discharge is not provided.
- the object of the present invention is a method of the beginning mentioned genus to create the reliable to pore-free borated surfaces leads and is therefore suitable for an industrial series application.
- the method according to the invention in its various alternatives described in more detail. Extensive tests have shown that it in plasma processing essential on the selection of the parameters of the generation of the arrives at the treatment room of the reactor. It was surprisingly found that these parameters should advantageously be selected such that an increased proportion of excited boron particles in the plasma is obtained. Contains that Plasma larger proportions of excited boron, this leads to low-pore layers. This was able to develop the method according to the invention for example by optical emission spectroscopy or plasma analysis be detected. In contrast, are BCI particles with high excitation in the plasma Containing content, then this leads to pore-rich layers resulting from those already above reasons mentioned should be avoided.
- the inventors were able to Research has found that various parameters regarding both Generation of the plasma as well as with regard to the individual components in the contained in the gas medium to be supplied, the desired content of can influence excited boron particles. It is important that certain Thresholds of excited boron in plasma can be reached to the desired level to achieve a low-pore layer.
- the glow discharge preferably with a pulsed DC voltage.
- the duty cycle is defined as the ratio between the time length of the voltage pulse to the subsequent pulse pause the desired generation of an increased content of excited boron particles and thus controlling the process for plasma generation in the desired sense allows.
- this should Duty cycle can be greater than 1.1, preferably it is in the range between about 1.25: 1 to 5: 1, more preferably in the range between 1.5: 1 and 3.5: 1.
- the period is also d. H. the sum of the duration of the Voltage pulse and the pulse pause at below about 230 ⁇ s and in particular ⁇ 50 ⁇ s.
- the period duration is more preferably in the method according to the invention according to a variant below about 230 ⁇ s and above 50 ⁇ s, e.g. B. at about 210 ⁇ s.
- the applied for the pulsed direct current to generate the glow discharge is preferably in the range between about 500 volts and about 1000 volts, preferably in the range between about 600 volts and about 900 volts, more preferably in the range between about 650 volts and about 800 volts. It was also found that when working with a higher voltage, the use of a longer pulse pause is advantageous. It but can also be preferably within the achieve a good result in the above-mentioned voltage ranges, with here also the Composition of the individual components of the reactor Gas medium can exert an influence.
- first component of the gas medium fed to the reactor is a boron donor medium Form of a boron trihalide, e.g. B. boron trichloride or boron trifluoride.
- a boron trihalide e.g. B. boron trichloride or boron trifluoride.
- gaseous hydrogen e.g. B. boron trichloride or boron trifluoride
- a noble gas is used as the third component of the gas medium, z. B. Argon. It was found that when argon is used as the third component, too even when using lower voltages within the scope of the invention Good boride layers can be produced.
- the content of boron trihalide as boron donor medium in the supplied gas medium usually affects the results of the method according to the invention.
- the salary of boron trihalide must not be too low and should generally not be below 1 vol .-%, since then usually no suitable boride layer is obtained.
- Boron trihalide content in the range from about 2% by volume to 50% by volume, with at However, it should be noted that high levels are relatively high Boron trihalide loss. This boron trihalide loss is found in the exhaust gas from the Reactor again and thus also leads to an increased effort in disposal or cleaning the exhaust gas.
- the setting of the desired parameters to achieve the desired effect can one z. B. make so that the proportion of excited boron particles in the plasma determined analytically and then one or more of the process parameters for generation glow discharge such as voltage, duty cycle, frequency, temperature, pressure etc. changed accordingly.
- the generation of Make boride layer in several stages, z. B. in a first stage works at a lower treatment temperature, thereby also for the Pore formation to avoid responsible halide formation in plasma.
- the first stage of the process is then first of all a thinner one closed boride layer that is more resistant to corrosive attack.
- you can then in a second treatment stage Raise the treatment temperature, thereby the diffusion of the boron particles and thus the Favor formation of a layer with increasing layer thickness.
- the treatment temperature changes, it should be noted that also the choice of the other process parameters has to be made in such a way that a possible increased content of excited boron particles is obtained in the plasma Favor boride formation reaction and avoid a corrosive attack.
- the current which can be set via the plasma generally has a significant influence in the context of the method according to the invention.
- the influencing of the layer characteristics or the suppression of pore formation, caused by the chlorine species present in the treatment atmosphere, and the favoring of the boride formation, as two competing reactions, are determined via this and the other plasma parameters.
- a plasma state can be achieved via a defined voltage, which is characterized by a high particle density of boron-releasing species, so that the boride formation takes place preferentially.
- the analysis of the plasma states can be carried out, for example, using optical emission spectroscopy.
- the signals for the excited boron, the excited BCI and the Cl + signal can be used to optimize the layer characteristics.
- Procedures in which the analysis methods show high B signals have proven to be favorable. This is possible, for example, with voltages in a medium range of preferably about 650 volts to 800 volts, the content of boron trihalide in the gas medium and the pulse duty factor of the pulsed direct current also playing a role.
- the method according to the invention is suitable for industrial applications and could be developed for series production. Compared to other known boriding processes of the type mentioned at the outset, which work with solid boron dispensing media, plasma working with a gaseous boron dispensing medium shows enormous potential for improvement.
- the handling of the components to be treated could be reduced to a minimum.
- the method according to the invention is suitable for automation. By changing the treatment time, a change in the gas composition is possible within the scope of the method according to the invention, so that the layer formation can be influenced thereby, special attention being paid to avoiding the formation of FeB. Furthermore, the method according to the invention takes account of the environmental concept, since the boroning agent residues to be disposed of can be minimized.
- Industrial areas of application for the method according to the invention are e.g. B. Boronizing of metal parts to increase the wear resistance of the surfaces of components, which are subject to particularly high abrasive or adhesive loads.
- the procedure according to the invention is suitable for. B. for use on components in the automotive industry for example for gears, hydraulic tappets, camshafts, oil pump drives z. B. with crossed axes, helical gears, continue for extruder screws and others Components that are exposed to increased stress.
- FIG. 1 shows a diagram of the Plant structure of a plant as used in the method according to the invention Production of a boride layer on a surface can be used by plasma working is.
- the system comprises a reactor 10 with a treatment room 11 in which the Plasma is generated.
- the treatment room 11 of the reactor 10 is loaded with a boron donor medium, which via a gas inlet 12 and the supply line 13 in the Treatment room 11 arrives.
- these components are Boron trihalide, e.g. B.
- the second component is Hydrogen gas, which is supplied via the branch line 15, which is also in the Feed line 13 opens out.
- the third component is an inert gas, e.g. B. argon that over the branch line 16 is fed, which also opens into the feed line 13.
- mass flow meters 17, 18 and 19 by means of which the flow of the respective component of the treatment gas is adjustable and measurable.
- the reactor 10 further comprises a charging plate 20 which is located in the reactor space 11 located and rests on two support insulators and the live support (not ) Shown.
- the supply of voltage for generating the glow discharge takes place via the voltage supply line 21 shown schematically
- Plasma generator delivers a pulsed DC voltage with a variable Pulse width or pulse pause as will be explained further below.
- the composition and the flow of the treatment gas are determined using the Mass flow meters 17, 18, 19 set.
- the measurement of the treatment pressure takes place via a gas meter independent pressure gauge and is also computer-controlled.
- the pressure measurement and pressure control is carried out using the in the scheme with 22 designated device, the line 23 with the Treatment room 11 is connected.
- the pressure control 22 is connected to this line 23 connected downstream a vacuum pump 24.
- This vacuum pump 24 downstream of this device is a device 25 for Exhaust gas cleaning, which ensures adequate exhaust gas treatment.
- the temperature of the plasma generator is regulated via the Temperature control device 26 and the line 27.
- the system according to the invention also has an additional heater 28 which in Reactor 10 is housed to achieve the desired treatment temperature in the Treatment room 11.
- the method according to the invention for producing a boride layer works preferably in the low pressure range, e.g. B. in the range of 1 to 10 hPa, and is by supports an electrical activation of the gas atmosphere.
- the ones to be treated (Boronizing) components are cathodically against the container wall of the Treatment room switched.
- the treatment temperature depends on that too boronizing material of the respective components and is, for example, above 700 ° C, preferably at 800 ° C or above.
- a pulsed DC voltage is preferably applied in order to enable the surface to be activated by the noble gas ion bombardment before the treatment phase.
- active excited boron particles are generated during the treatment, which reach the surface of the component and form borides there primarily by diffusion.
- the reduction of the halogen present in the atmosphere, which is generated from the boron trihalide, is favored by the atomic hydrogen generated in the plasma, which is produced from the H 2 gas supplied.
- the diagram according to FIG. 2 shows an example of a possible voltage curve in FIG Dependence on the time for a pulsed direct current as it is for a
- the inventive method is particularly advantageous.
- the voltage is z. B. in a middle range at 650 volts, the voltage pulse for example 160 microseconds is maintained and the pulse pause is, for example, 50 microseconds.
- the pulse pause is thus about a factor of 3 shorter than the duration of the DC voltage pulse.
- the Period duration in the exemplary embodiment is 210 microseconds and thus is Frequency 4.762 kHz.
- the duty cycle is defined as the ratio of the length of the
- the pulse duration for the pulse pause within a pulse is included in the exemplary embodiment 3.2. It has been found that using a relatively high voltage longer pulse pause required. When using argon in the treatment gas, but also at relatively low voltages, e.g. B. good in the range above 500 volts Get results.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Chemical Vapour Deposition (AREA)
- Electron Sources, Ion Sources (AREA)
- Primary Cells (AREA)
- Apparatus For Radiation Diagnosis (AREA)
- Plasma Technology (AREA)
Description
- Fig. 1
- eine schematisch vereinfachte Darstellung einer erfindungsgemäßen Anlage zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren
- Fig. 2
- ein Diagramm betreffend die zeitliche Änderung der Spannung bei dem gepulsten Gleichstrom der für ein erfindungsgemäßes Verfahren verwendet wird.
Claims (17)
- Verfahren zur Erzeugung einer Boridschicht auf einer Oberfläche durch Plasmaborieren, bei dem man einem Behandlungsraum eines Reaktors ein ein Borspendermedium enthaltendes Gasmedium zuführt und in dem Reaktor eine Glimmentladung erzeugt, dadurch gekennzeichnet, dass man in der Glimmentadung die Menge mindestens eines angeregten Borspendermediumprodukts bestimmt und die Parameter der Erzeugung des in dem Behandlungsraum (11) des Reaktors (10) erzeugten Plasmas so wählt, dass eine Mindest- und/oder Höchstmenge des bzw. der bestimmten angeregten Borspendermediumprodukte und/oder ein Mindest- und/oder Höchstwert einer Relation mit einem oder mehreren der bestimmten angeregten Borspendermediumprodukte eingehalten wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass man zur Erzeugung der Glimmentladung eine gepulste Gleichspannung mit einem Verhältnis zwischen der zeitlichen Länge des Spannungspulses zu der nachfolgenden Pulspause größer als 1,1 verwendet.
- Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man zur Erzeugung der Glimmentladung eine Gleichspannung mit einer Periodendauer kleiner als 230 µs verwendet.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man zunächst in einer ersten Stufe bei einer geringeren Behandlungstemperatur arbeitet, um die für die Bildung von Poren verantwortliche Halogenidbildung im Plasma zu vermeiden und eine zunächst dünnere, insbesondere geschlossene Boridschicht zu erzeugen, und man im Anschluss daran in einer zweiten Behandlungsstufe mit höherer Behandlungstemperatur arbeitet.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Menge des angeregten Borspendermediums zumindest relativ bestimmt wird.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Menge des angeregten Borspendermediums spektroskopisch bestimmt wird.
- Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass als angeregtes Borspendermediumprodukt zumindest angeregtes Bor bestimmt wird.
- Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass zur Bildung des Mindest und/oder Höchstwertes die bestimmte Menge des angeregten Borspendermediums mit einer bestimmten Menge mindestens eines weiteren Borspendermediumproduktes ins Verhältnis gesetzt wird.
- Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man ein Gasmedium zuführt, das als Borspendermedium ein Bortrihalogenid in einem Gehalt größer als etwa 1 Vol.-% und daneben Wasserstoff sowie gegebenenfalls als Edelgas enthält.
- Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass man zur Erzeugung des Plasmas eine gepulste Gleichspannung mit einem Verhältnis zwischen der zeitlichen Länge des Spannungspulses zu der nachfolgenden Pulspause im Bereich von etwa 1,1 : 1 bis 5 : 1, vorzugsweise im Bereich von etwa 1,5 : 1 bis 3,5 : 1 verwendet.
- Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass man zur Erzeugung des Plasmas eine gepulste Gleichspannung mit einer Periodendauer kleiner als etwa 210 µs verwendet.
- Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Periodendauer ≥ 50 µs beträgt.
- Verfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass man zur Erzeugung der Glimmentladung eine gepulste Gleichspannung im Bereich zwischen etwa 500 Volt bis etwa 1000 Volt, vorzugsweise im Bereich zwischen etwa 650 Volt und etwa 800 Volt verwendet.
- Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass man in einem Niederdruckbereich zwischen etwa 0,5 und etwa 15 hPa arbeitet, vorzugsweise im Bereich zwischen etwa 1 und etwa 10 hPa.
- Verfahren nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass man ein Gasmedium zuführt, das ein Bortrihalogenid mit einem Gehalt zwschen 2 Vol.-% bis etwa 50 Vol.-%, vorzugsweise mit einem Gehalt zwischen etwa 2 Vol.-% bis etwa 10 Vol-.% enthält.
- Verfahren nach einem der Ansprüche 1 bis 15, dadurch gekennzeichnet, dass man ein Gasmedium zuführt, das bis 20 Vol.-% eines Edelgases, vorzugsweise Argon, 2 Vol.-% bis 50 Vol.-% an Bortrihalogenid, vorzugsweise 2 Vol.-% bis 10 Vol.-% an Bortrihalogenid und im Übrigen Wasserstoff enthält.
- Verfahren nach einem der Ansprüche 1 bis 16, dadurch gekennzeichnet, dass man als Borspendermedium BCl3 oder BF3 verwendet.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01110904A EP1143031A3 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19755595 | 1997-12-15 | ||
DE19755595 | 1997-12-15 | ||
PCT/EP1998/008079 WO1999031291A2 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01110904A Division EP1143031A3 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
EP01110904.8 Division-Into | 2001-05-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1044289A2 EP1044289A2 (de) | 2000-10-18 |
EP1044289B1 true EP1044289B1 (de) | 2002-03-27 |
Family
ID=7851902
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01110904A Ceased EP1143031A3 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
EP98965249A Expired - Lifetime EP1044289B1 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01110904A Ceased EP1143031A3 (de) | 1997-12-15 | 1998-12-11 | Plasmaborierung |
Country Status (8)
Country | Link |
---|---|
US (1) | US6783794B1 (de) |
EP (2) | EP1143031A3 (de) |
JP (1) | JP4588213B2 (de) |
KR (1) | KR100583262B1 (de) |
CN (1) | CN1198953C (de) |
AT (1) | ATE215132T1 (de) |
DE (1) | DE59803574D1 (de) |
WO (1) | WO1999031291A2 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE524493C2 (sv) * | 2002-02-25 | 2004-08-17 | Telia Ab | Uppskattningsenhet och metod för att bestämma positionen för en mobil station i ett mobilt kommunikationssystem |
JP2009512778A (ja) * | 2005-09-22 | 2009-03-26 | スカフコ エンジニアリング アンド マニュファクチャリング, インコーポレイテッド | プラズマホウ化方法 |
MX2008013386A (es) * | 2006-04-20 | 2009-01-26 | Skaff Corp Of America Inc | Partes mecanicas que tienen resistencia incrementada contra el desgaste. |
AU2008228694B2 (en) * | 2007-03-22 | 2012-03-08 | Skaff Corporation Of America, Inc. | Mechanical parts having increased wear-resistance |
US8338317B2 (en) * | 2011-04-06 | 2012-12-25 | Infineon Technologies Ag | Method for processing a semiconductor wafer or die, and particle deposition device |
CN104233425B (zh) * | 2014-09-29 | 2017-01-25 | 河海大学常州校区 | 微弧渗硼催化溶液和微弧渗硼溶液以及微弧渗硼方法 |
CN108220922B (zh) * | 2016-12-15 | 2020-12-29 | 东京毅力科创株式会社 | 成膜方法、硼膜以及成膜装置 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3677799A (en) * | 1970-11-10 | 1972-07-18 | Celanese Corp | Vapor phase boron deposition by pulse discharge |
JPS5118944A (ja) * | 1974-08-07 | 1976-02-14 | Suwa Seikosha Kk | Kisohokaho |
JPS56105627A (en) * | 1980-01-28 | 1981-08-22 | Fuji Photo Film Co Ltd | Manufacture of amorphous semiconductor |
DE3322341A1 (de) * | 1983-06-22 | 1985-01-03 | Siegfried Dr.-Ing. 5135 Selfkant Strämke | Verfahren und vorrichtung zur oberflaechenbehandlung von werkstuecken durch glimmentladung |
DE3908200C1 (de) * | 1989-03-14 | 1989-09-07 | Degussa Ag, 6000 Frankfurt, De | |
DE4003623A1 (de) | 1990-02-07 | 1991-08-08 | Kloeckner Ionon | Verfahren zur steuerung einer anlage zur plasmabehandlung von werkstuecken |
US5286534A (en) * | 1991-12-23 | 1994-02-15 | Minnesota Mining And Manufacturing Company | Process for plasma deposition of a carbon rich coating |
US5374456A (en) | 1992-12-23 | 1994-12-20 | Hughes Aircraft Company | Surface potential control in plasma processing of materials |
US5354381A (en) * | 1993-05-07 | 1994-10-11 | Varian Associates, Inc. | Plasma immersion ion implantation (PI3) apparatus |
FR2708624A1 (fr) * | 1993-07-30 | 1995-02-10 | Neuville Stephane | Procédé de dépôt d'un revêtement protecteur à base de pseudo carbone diamant amorphe ou de carbure de silicium modifié. |
JPH07286254A (ja) * | 1994-04-21 | 1995-10-31 | Sumitomo Metal Ind Ltd | 耐二次加工脆性に優れた鋼板およびその製造方法 |
JP3050361B2 (ja) * | 1994-07-19 | 2000-06-12 | 株式会社ライムズ | 金属部材のイオン窒化方法 |
DE4427902C1 (de) * | 1994-08-06 | 1995-03-30 | Leybold Durferrit Gmbh | Verfahren zum Aufkohlen von Bauteilen aus kohlungsfähigen Werkstoffen mittels einer impulsförmig betriebenen Plasmaentladung |
US5578725A (en) | 1995-01-30 | 1996-11-26 | Regents Of The University Of Minnesota | Delta opioid receptor antagonists |
JPH0982495A (ja) * | 1995-09-18 | 1997-03-28 | Toshiba Corp | プラズマ生成装置およびプラズマ生成方法 |
DE19602639A1 (de) | 1996-01-25 | 1997-07-31 | Kempten Elektroschmelz Gmbh | Verfahren zur Herstellung von verschleißfesten Boridschichten auf metallischen Werkstoffoberflächen |
US6306225B1 (en) * | 1996-01-25 | 2001-10-23 | Bor Tec Gmbh | Process for producing wear-resistant boride layers on metallic material surfaces |
DE19629877C1 (de) * | 1996-07-24 | 1997-03-27 | Schott Glaswerke | CVD-Verfahren und Vorrichtung zur Innenbeschichtung von Hohlkörpern |
US5654043A (en) * | 1996-10-10 | 1997-08-05 | Eaton Corporation | Pulsed plate plasma implantation system and method |
US6101971A (en) * | 1998-05-13 | 2000-08-15 | Axcelis Technologies, Inc. | Ion implantation control using charge collection, optical emission spectroscopy and mass analysis |
US20040016402A1 (en) * | 2002-07-26 | 2004-01-29 | Walther Steven R. | Methods and apparatus for monitoring plasma parameters in plasma doping systems |
-
1998
- 1998-12-11 JP JP2000539186A patent/JP4588213B2/ja not_active Expired - Fee Related
- 1998-12-11 EP EP01110904A patent/EP1143031A3/de not_active Ceased
- 1998-12-11 KR KR1020007006436A patent/KR100583262B1/ko not_active IP Right Cessation
- 1998-12-11 CN CNB988121832A patent/CN1198953C/zh not_active Expired - Fee Related
- 1998-12-11 WO PCT/EP1998/008079 patent/WO1999031291A2/de active IP Right Grant
- 1998-12-11 AT AT98965249T patent/ATE215132T1/de not_active IP Right Cessation
- 1998-12-11 DE DE59803574T patent/DE59803574D1/de not_active Expired - Lifetime
- 1998-12-11 EP EP98965249A patent/EP1044289B1/de not_active Expired - Lifetime
-
2000
- 2000-06-15 US US09/594,905 patent/US6783794B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
ATE215132T1 (de) | 2002-04-15 |
JP2002508448A (ja) | 2002-03-19 |
DE59803574D1 (de) | 2002-05-02 |
CN1282383A (zh) | 2001-01-31 |
KR100583262B1 (ko) | 2006-05-25 |
EP1143031A3 (de) | 2004-04-28 |
US6783794B1 (en) | 2004-08-31 |
KR20010033075A (ko) | 2001-04-25 |
JP4588213B2 (ja) | 2010-11-24 |
CN1198953C (zh) | 2005-04-27 |
EP1143031A2 (de) | 2001-10-10 |
WO1999031291A3 (de) | 1999-09-10 |
WO1999031291A2 (de) | 1999-06-24 |
EP1044289A2 (de) | 2000-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102006023018A1 (de) | Plasmaverfahren zur Oberflächenbehandlung von Werkstücken | |
DE3144192C2 (de) | Verfahren zum Bedampfen einer Oberfläche mit Hartstoffen und Anwendung des Verfahrens | |
DE3117299C3 (de) | Verfahren zur Herstellung eines mit einem Hartstoff beschichteten Gegenstandes | |
DE3327103C2 (de) | Sinterverfahren für Preßkörper | |
DE69227313T2 (de) | Verfahren und vorrichtung zur behandlung von bauteilen in einem gasentladungsplasma | |
DE3513014C2 (de) | Verfahren zur Behandlung der Oberfläche von Werkstücken | |
DE19702187C2 (de) | Verfahren und Einrichtung zum Betreiben von Magnetronentladungen | |
EP0668938B1 (de) | Werkzeug und verfahren zur beschichtung eines werkzeuggrundkörpers | |
EP0990061A1 (de) | Verfahren und einrichtung zum vakuumbeschichten eines substrates | |
EP0432528B1 (de) | Verfahren zur Erzeugung von Schichten aus harten Kohlenstoffmodifikationen und Vorrichtung zur Durchführung des Verfahrens | |
DE19526387A1 (de) | Doppelt beschichteter Stahlverbundgegenstand und Verfahren zu dessen Herstellung | |
DE3841730C2 (de) | Verfahren zum Beschichten eines metallischen Grundkörpers mit einem nichtleitenden Beschichtungsmaterial | |
DE3614384A1 (de) | Verfahren zur beschichtung von substraten in einer vakuumkammer | |
EP1044289B1 (de) | Plasmaborierung | |
EP1032943A2 (de) | Verfahren zur erzeugung eines plasmas durch einstrahlung von mikrowellen | |
EP0303161A2 (de) | Verfahren zum Aufbringen von Überzügen auf Gegenstände mittels magnetfeldunterstützter Kathodenzerstäubung im Vakuum | |
EP1194611A1 (de) | Anlage und verfahren zur vakuumbehandlung bzw. zur pulverherstellung | |
DE4228499C1 (de) | Verfahren und Einrichtung zur plasmagestützten Beschichtung von Substraten | |
DE4427902C1 (de) | Verfahren zum Aufkohlen von Bauteilen aus kohlungsfähigen Werkstoffen mittels einer impulsförmig betriebenen Plasmaentladung | |
EP0882811A1 (de) | Verfahren zur Aufkohlung metallischer Werkstücke in einem Vakuum-Ofen | |
DE102009061065A1 (de) | Verfahren zur Beschichtung eines Subtrates in einer Vakuumkammer mit einem rotierenden Magnetron | |
DE4238993C1 (de) | ||
DE3390522C2 (de) | Spanendes Werkzeug und Verfahren zu dessen Herstellung | |
DE3030454C2 (de) | Vorrichtung zur großflächigen Abscheidung von haftfesten, insbesondere harten Kohlenstoffschichten | |
DE19815019A1 (de) | Verfahren zur Herstellung von Aluminiumnitridschichten auf Bauteilen aus Aluminiumwerkstoffen auf der Grundlage des Plasmanitrierens |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT DE ES FR GB IT PT SE |
|
17P | Request for examination filed |
Effective date: 20000717 |
|
17Q | First examination report despatched |
Effective date: 20010125 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT DE ES FR GB IT PT SE |
|
REF | Corresponds to: |
Ref document number: 215132 Country of ref document: AT Date of ref document: 20020415 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 59803574 Country of ref document: DE Date of ref document: 20020502 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020627 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020627 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20020614 |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20020925 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021211 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20021230 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20071217 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20071121 Year of fee payment: 10 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20081211 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081211 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20110117 Year of fee payment: 13 Ref country code: DE Payment date: 20110111 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 59803574 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20120831 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 59803574 Country of ref document: DE Effective date: 20120703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120703 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20120102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081211 |