WO2006029743A1 - Method and device for applying an electrically conductive transparent coating to a substrate - Google Patents
Method and device for applying an electrically conductive transparent coating to a substrate Download PDFInfo
- Publication number
- WO2006029743A1 WO2006029743A1 PCT/EP2005/009575 EP2005009575W WO2006029743A1 WO 2006029743 A1 WO2006029743 A1 WO 2006029743A1 EP 2005009575 W EP2005009575 W EP 2005009575W WO 2006029743 A1 WO2006029743 A1 WO 2006029743A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- microwave
- substrate
- plasma
- coating
- gas
- Prior art date
Links
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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/029—Graded interfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/511—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using microwave discharges
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32192—Microwave generated discharge
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/02—Details
- H01J2237/022—Avoiding or removing foreign or contaminating particles, debris or deposits on sample or tube
Definitions
- TCO electrically conductive transparent coating or TCO coating
- plasma pulse CVD plasma-impulse-chemical vapor deposition
- Coatings deposited from a plasma phase which is generated in the plasma chamber or coating chamber of a reactor device by coupling microwave pulses of suitable intensity and pulse duration via an associated microwave coupling device.
- the composition of the coatings can be controlled as required by suitable choice of the process gas used for plasma formation. This usually comprises a layer-specific gas mixture with one or more precursor gases for the actual layer formation, one or more doping gases and one or more carrier gases. If appropriate, it can also be changed in its chemical composition between individual microwave pulses so that an application-specific one consisting of a plurality of different layers is provided during a process sequence or coating process customized multilayer system is deposited. Due to the pulsed mode of operation, the layer construction takes place only in small steps, so that very dense and homogeneous layers or layer systems are formed. It also enables very low process temperatures, so that PICVD processes are particularly suitable for coating plastics.
- DE 101 39 305 A1 discloses a PICVD process for producing a composite material by depositing at least one barrier coating on one side of a suitable substrate material, e.g. one
- the barrier coating can hereby including, but not limited to, electrically conductive layers and SnO x layers with xe [0.2].
- DE 39 26 023 C2 discloses a PICVD coating process for the preparation of the electrical and metallic layers, e.g. be used in optics and optical fibers. An apparatus for carrying out this method is also described.
- Einkopplungs made described, one of which is exposed to the coating space and between this and an adjacent etching space is movable.
- This microwave coupling window is cleaned during a coating process running in the coating space by etching away the deposited on it undesirable coating by means of a suitable etching gas in the etching, so that an excessive layer formation is avoided and in particular at high microwave intensities longer operating times can be achieved.
- the reactor described is used for depositing large-area semiconductor layers by means of a MWPCVD method (microwave plasma CVD method). There is no deposition of conductive layers.
- the object of the present invention is to provide a simple and inexpensive PICVD process for depositing electrically conductive transparent coatings or TCO coatings which allows long operating times with a substantially constant plasma intensity.
- the TCO coatings should have a transmission T of more than about 80% in the visible spectral range (VIS), while their specific resistance p should be lower than about 10 ⁇ -cm.
- the object is also to provide a reactor device for carrying out this method.
- the undesired formation of an electrically conductive coating on the microwave coupling device is deliberately suppressed by means of a TCO protection device, so that the microwaves can pass through the microwave coupling device substantially unhindered even during prolonged periods of operation and in the plasma chamber - in difference to conventional PICVD methods - always a sufficiently high microwave intensity for plasma formation is available.
- a microwave-permeable covering or separating device can be used, which is located between the plasma chamber and the microwave coupling device arranged and optionally cleaned or replaced at an inadmissible thickness coating at certain intervals.
- Coupling device can in this case, for example, completely covered or masked with the covering or separating substantially. According to the invention, however, a substantially plasma-tight separating wall-shaped separation device for the plasma chamber can also be used as coating protection for the microwave coupling device.
- a suitable film such as a Kapton film, or an adhesive tape can be used.
- the film may in this case according to the invention optionally also be formed as a kind of continuous film and during a coating operation by means of a suitable transport device, such as. a winding and unwinding or transport rollers, with a certain speed continuously or quasi ⁇ be moved past the microwave coupling device or the plasma chamber, so that an impermissibly strong layer formation is reliably avoided.
- a suitable transport device such as. a winding and unwinding or transport rollers
- the substrate to be coated itself can also be used as a covering or separating device, in particular by arranging it in such a way that it shields the microwave coupling device essentially plasma-tight with respect to the plasma space.
- the substrate side facing the plasma chamber is provided with the desired electrically conductive coating, while the substrate side facing away from the plasma and the microwave coupling device facing substrate side and the Microwave coupling device remain uncoated.
- the substrate is coated on one side. By subsequently turning the substrate, a two-sided coating may optionally also be applied.
- This method variant according to the invention can be used, for example, in the coating of a substantially planar substrate in a PICVD planar installation with a microwave coupling window. In this case, the substrate is placed or applied with its side not to be coated onto the microwave coupling window, so that it is almost completely or completely covered and the formation of an undesirable TCO coating is reliably prevented.
- the unwanted formation of an electrically conductive coating on the microwave coupling device according to the invention can also be suppressed by a suitable control of the gas composition or the gas guide in the plasma chamber.
- a suitable control of the gas composition or the gas guide in the plasma chamber can also be suppressed by a suitable control of the gas composition or the gas guide in the plasma chamber.
- a type of sealing gas arrangement can be used in which the microwave coupling device can be flowed around by means of a suitable gas supply device from the respective carrier gas.
- the precursor gas can be passed by means of a corresponding gas supply device past the microwave copying device directly onto the substrate to be coated. By both measures, the precursor gas is kept away from the microwave coupling device and the undesired formation of a conductive coating is effectively suppressed there.
- the formation of an electrically conductive coating on the microwave Coupling device by cooling the microwave coupling device and / or the protective device, such as the covering or separating device, by means of an associated cooling device to a sufficiently low
- Temperature level can be suppressed, in which only an electrically or only slightly conductive layer separates, which allows the microwaves pass substantially unhindered.
- the plasma formation is thus not significantly impeded or even prevented even with longer operating times.
- the actual process temperature in the plasma chamber and the substrate temperature remain virtually unimpaired by this cooling measure, so that the substrate itself is provided with the desired electrically conductive coating.
- Coupling device and / or the protective device are in this case preferably cooled to a temperature of at least about 40 0 C.
- sufficiently cool air can be supplied, for example by the cooling device from the waveguide.
- the electrically conductive coating is preferably deposited at a substrate temperature between about 50 0 C and 320 0 C, wherein in particular plastic substrates substrate temperatures of less than about 100 0 C are used.
- the PICVD process according to the invention is particularly suitable for coating rigid or flexible plastic substrates.
- it can also be advantageously used for coating inorganic substrates, such as glass substrates or a glass ceramic.
- the Substrate may also be a film which is identical to the protective device.
- the (plastic) film would (quasi) -continuously coated.
- an adhesion-promoting layer or an adhesion-promoting layer system is first applied thereto before the application of the electrically conductive coating.
- the composition of the process gas is thereby changed during the coating process so as to form a gradient layer or a gradient layer system having a substantially organic composition on the substrate side and a wesentichen inorganic composition on the TCO coating side, which is identical to the substrate or to the TCO coating is selected.
- the precursor for the primer layer preferably comprises hexamethyldisiloxane (HMDSO)
- the described PICVD process according to the invention preferably applies a conductive coating which comprises indium tin oxide or else ITO (In 2 O 3 : SnO 2 ), doped ZnO 2 or doped SnO 2 .
- a carrier gas is preferably oxygen
- tin chloride SnCl 4 or tetramethyltin (TMT) can be used as precursor gas for doped SnO 2 .
- doping gas tetrafluoromethane or fluorine has been proven.
- precursor gas for ITO coatings trimethylindium In (CH 3 ) 3 or indium perchlorate In (ClO 4 ) 3 or indium acetylacetonate IN (C O H 7 O 2 ) 3 with tin chloride SnCl 4 or tetramethyltin Sn (CH 3 ) 3 can be used.
- a precursorgas for ZnOrF can dimethylzinc Zn (CH 3 ) 2 or zinc sulfate ZnSnO 4 with CF 4 or F 2 can be used as doping gas.
- the PICVD process according to the invention is preferably operated continuously or quasi-continuously.
- the present PICVD process applies TCO coatings with a transmission T of greater than about 80% in the visible spectral range (VIS) and a resistivity n of less than about 10 ⁇ * cm.
- the plasma chamber is provided with a microwave coupling device, such as a microwave coupling window or a quartz tube, which is connectable or connected via a microwave conductor with an associated microwave generator for generating microwave pulses of suitable intensity and pulse duration.
- the microwave coupling device according to the invention is protected by a microwave transparent TCO protection device against the undesired formation of an electrically conductive coating.
- a holding, guiding or transport device for a substrate to be coated is also provided.
- the protective device comprises a microwave-permeable covering or separating device, such as a film or an adhesive tape, for example is arranged between the plasma chamber and the microwave coupling device.
- the covering or separating device is preferably designed to be exchangeable or cleanable. It can be applied or glued directly to the microwave coupling device. However, it can also be designed as a plasma-tight partition or separation device for the plasma chamber or coating space. It can also be a transport device for the covering or separating device, such as a winding and unwinding be provided.
- the protective device can also comprise a second gas supply device for holding or guiding device and / or for microwave coupling device.
- the protective device can also be provided with a cooling device for itself and / or for the microwave coupling device.
- the reactor device may in particular also comprise a control device for controlling the method sequence.
- the important characteristic data of some TCO layers applied by the PICVD method according to the invention are compiled by way of example, which have been applied in the plasma or coating space of a PICVD planar reactor of the type described to an essentially planar glass or plastic substrate.
- a PICVD planar reactor of the type described to an essentially planar glass or plastic substrate.
- the plastic polycarbonate (PC) and a polyimide were used, which is commercially available under the trade name Kapton ® .
- the PICVD planar reactor included a microwave launch window for launching the required microwaves generated in an associated microwave generator and delivered to the microwave launch window via a microwave waveguide.
- the pulse duration and the pulse pause of the coupled-in microwave pulses were 1 to 4 ms and 10 to 80 ms, respectively, with a microwave power of 3 to 9 kW.
- the total gas flow through the plasma chamber was 100-400 standard cubic centimeters per minute (sccm).
- the carrier gas used was 100-400 sccm oxygen, which was doped with 0.25-4 sccm CF 4 .
- the precursor gas used was tin chloride or tetramethyltin (TMT) at a concentration between 1-66.7% in the carrier gas.
- the substrate temperature T 3 was between 100 0 C for the PC substrates and a maximum of 320 0 C for a glass substrate.
- the substrates to be coated were placed or applied with their uncoated side on the microwave coupling window so that it was completely covered and the formation of an undesirable TCO coating was reliably prevented there.
- the substrate side facing the plasma space was provided with the desired electrically conductive SnC: F coating having the following properties.
- an HMDSO adhesion-promoting gradient layer was first applied before the deposition of the SnO 2 : F coating.
- the layer thicknesses d are 0.2-0.7 ⁇ m.
- TCO layers with a layer thickness d of up to about 8 ⁇ m were also deposited with the described method according to the invention.
- TCO layers having a thickness d of only about 0.1 ⁇ m were also produced.
- the resistivity p of the given TCO layers is between 6-10 "4 ⁇ -cm for the glass substrate and 0.16 ⁇ -cm for a PC substrate.
- TCO layers having a sheet resistance R sq of up to about 10 8 ⁇ were deposited.
- the transmission T of the TCO layers in the visible spectral range (VIS) is in some cases more than 80%.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05784706A EP1797217A1 (en) | 2004-09-15 | 2005-09-07 | Method and device for applying an electrically conductive transparent coating to a substrate |
JP2007531637A JP2008513601A (en) | 2004-09-15 | 2005-09-07 | Method and device for depositing a conductive transparent coating on a substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200410045046 DE102004045046B4 (en) | 2004-09-15 | 2004-09-15 | Method and device for applying an electrically conductive transparent coating to a substrate |
DE102004045046.3 | 2004-09-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006029743A1 true WO2006029743A1 (en) | 2006-03-23 |
Family
ID=35385197
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/009575 WO2006029743A1 (en) | 2004-09-15 | 2005-09-07 | Method and device for applying an electrically conductive transparent coating to a substrate |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1797217A1 (en) |
JP (1) | JP2008513601A (en) |
CN (1) | CN101044263A (en) |
DE (1) | DE102004045046B4 (en) |
WO (1) | WO2006029743A1 (en) |
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US8512796B2 (en) | 2009-05-13 | 2013-08-20 | Si02 Medical Products, Inc. | Vessel inspection apparatus and methods |
WO2013159642A1 (en) * | 2012-04-23 | 2013-10-31 | 光达光电设备科技(嘉兴)有限公司 | Spraying nozzle for chemical vapor deposition process and method for improving process uniformity |
US9272095B2 (en) | 2011-04-01 | 2016-03-01 | Sio2 Medical Products, Inc. | Vessels, contact surfaces, and coating and inspection apparatus and methods |
US9458536B2 (en) | 2009-07-02 | 2016-10-04 | Sio2 Medical Products, Inc. | PECVD coating methods for capped syringes, cartridges and other articles |
US9545360B2 (en) | 2009-05-13 | 2017-01-17 | Sio2 Medical Products, Inc. | Saccharide protective coating for pharmaceutical package |
US9554968B2 (en) | 2013-03-11 | 2017-01-31 | Sio2 Medical Products, Inc. | Trilayer coated pharmaceutical packaging |
US9664626B2 (en) | 2012-11-01 | 2017-05-30 | Sio2 Medical Products, Inc. | Coating inspection method |
US9662450B2 (en) | 2013-03-01 | 2017-05-30 | Sio2 Medical Products, Inc. | Plasma or CVD pre-treatment for lubricated pharmaceutical package, coating process and apparatus |
US9764093B2 (en) | 2012-11-30 | 2017-09-19 | Sio2 Medical Products, Inc. | Controlling the uniformity of PECVD deposition |
US9863042B2 (en) | 2013-03-15 | 2018-01-09 | Sio2 Medical Products, Inc. | PECVD lubricity vessel coating, coating process and apparatus providing different power levels in two phases |
US9878101B2 (en) | 2010-11-12 | 2018-01-30 | Sio2 Medical Products, Inc. | Cyclic olefin polymer vessels and vessel coating methods |
US9903782B2 (en) | 2012-11-16 | 2018-02-27 | Sio2 Medical Products, Inc. | Method and apparatus for detecting rapid barrier coating integrity characteristics |
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US10189603B2 (en) | 2011-11-11 | 2019-01-29 | Sio2 Medical Products, Inc. | Passivation, pH protective or lubricity coating for pharmaceutical package, coating process and apparatus |
US10201660B2 (en) | 2012-11-30 | 2019-02-12 | Sio2 Medical Products, Inc. | Controlling the uniformity of PECVD deposition on medical syringes, cartridges, and the like |
US11066745B2 (en) | 2014-03-28 | 2021-07-20 | Sio2 Medical Products, Inc. | Antistatic coatings for plastic vessels |
US11077233B2 (en) | 2015-08-18 | 2021-08-03 | Sio2 Medical Products, Inc. | Pharmaceutical and other packaging with low oxygen transmission rate |
US11116695B2 (en) | 2011-11-11 | 2021-09-14 | Sio2 Medical Products, Inc. | Blood sample collection tube |
US11624115B2 (en) | 2010-05-12 | 2023-04-11 | Sio2 Medical Products, Inc. | Syringe with PECVD lubrication |
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JP5195354B2 (en) * | 2008-12-01 | 2013-05-08 | セイコーエプソン株式会社 | Optical element |
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DE3926023A1 (en) * | 1988-09-06 | 1990-03-15 | Schott Glaswerke | CVD COATING METHOD FOR PRODUCING LAYERS AND DEVICE FOR CARRYING OUT THE METHOD |
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-
2004
- 2004-09-15 DE DE200410045046 patent/DE102004045046B4/en not_active Expired - Fee Related
-
2005
- 2005-09-07 WO PCT/EP2005/009575 patent/WO2006029743A1/en not_active Application Discontinuation
- 2005-09-07 JP JP2007531637A patent/JP2008513601A/en active Pending
- 2005-09-07 EP EP05784706A patent/EP1797217A1/en not_active Withdrawn
- 2005-09-07 CN CNA200580035585XA patent/CN101044263A/en active Pending
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DE3938830A1 (en) * | 1988-11-24 | 1990-05-31 | Canon Kk | DEVICE FOR CHEMICAL MICROWAVE PLASMA VAPORIZATION |
DE4030900A1 (en) * | 1990-09-29 | 1992-04-02 | Bosch Gmbh Robert | METHOD AND DEVICE FOR COATING PARTS |
US5232507A (en) * | 1991-05-01 | 1993-08-03 | Canon Kabushiki Kaisha | Apparatus for forming deposited films with microwave plasma CVD method |
DE10112330A1 (en) * | 2000-09-29 | 2002-04-11 | Schott Glas | Optical waveguide and method for producing optical waveguides |
DE10054653A1 (en) * | 2000-11-03 | 2002-05-08 | Ver Foerderung Inst Kunststoff | Method and device for coating hollow bodies |
DE10139305A1 (en) * | 2001-08-07 | 2003-03-06 | Schott Glas | Composite material made of a substrate material and a barrier layer material |
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Also Published As
Publication number | Publication date |
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EP1797217A1 (en) | 2007-06-20 |
JP2008513601A (en) | 2008-05-01 |
DE102004045046A1 (en) | 2006-04-06 |
DE102004045046B4 (en) | 2007-01-04 |
CN101044263A (en) | 2007-09-26 |
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