EP1010473A2 - Vorrichtung und Verfahren zum Beschichten eines ebenen Substrates - Google Patents
Vorrichtung und Verfahren zum Beschichten eines ebenen Substrates Download PDFInfo
- Publication number
- EP1010473A2 EP1010473A2 EP99811153A EP99811153A EP1010473A2 EP 1010473 A2 EP1010473 A2 EP 1010473A2 EP 99811153 A EP99811153 A EP 99811153A EP 99811153 A EP99811153 A EP 99811153A EP 1010473 A2 EP1010473 A2 EP 1010473A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- substrate
- capillary gap
- medium
- module
- 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.)
- Granted
Links
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/02—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material to surfaces by single means not covered by groups B05C1/00 - B05C7/00, whether or not also using other means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
- B05C11/1002—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves
- B05C11/1007—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves responsive to condition of liquid or other fluent material
- B05C11/1013—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves responsive to condition of liquid or other fluent material responsive to flow or pressure of liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0254—Coating heads with slot-shaped outlet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S118/00—Coating apparatus
- Y10S118/04—Curtain coater
Definitions
- the invention relates to a device for coating a flat substrate, with a capillary gap Coating module, which capillary gap with a liquid Coating medium is filled and has an opening which is a surface to be coated of the substrate in comparison a small distance is to be passed so that deposits a layer on said surface.
- the invention also relates to a method for coating a Substrate, with a coating module on which the substrate is guided past with the surface to be coated and a layer of the coating medium on this surface deposits, the coating module during the coating Coating medium is supplied.
- a device of the type mentioned is in the prior art from US 5,650,196 and WO 94/25177.
- This device can be, for example, rectangular or round Panels with an even layer of varnish or other initially liquid media such as color filters or special ones Protective layers are provided.
- the use of this device is included in the area of thin film technology in particular the production of LCD screens, masks for semiconductor production and semiconductor or ceramic substrates.
- This device is particularly characterized by a high level of uniformity the coating thickness, especially on rectangular plates with low paint consumption.
- For coating the substrate with the surface to be coated facing down passed over the capillary gap which is designed such that the coating medium due to the capillarity of the gap automatically and at a particularly uniform speed is delivered later.
- Such a capillary action is, for example reached with a gap less than 0.5 mm wide is.
- the coating medium increases due to the capillary action against gravity in the gap automatically upwards and emerges at the opening of the capillary gap.
- Usual coating speeds are 5 to 15 mm / s. Because the volume flow through significantly the intermolecular binding forces can be determined do not significantly increase the coating speed.
- the invention has for its object a device to create the type mentioned, which has a significantly higher coating speed enabled, but still with little Material consumption ensures a uniform layer thickness.
- the task is in a generic device solved that the capillary gap is open at the bottom and over a Supply room is filled with coating medium and that Substrate under the opening of the gap with the one to be coated Surface is passed upwards.
- the device is the volume flow through the capillary gap not only determined by the intermolecular binding forces, but can be actively determined. This can be essential higher coating speeds, for example between 30 and 100 mm / s can be achieved. The higher coating speed accordingly enables higher production and thus a significant reduction in manufacturing costs.
- an overflow vessel which is connected to a liquid line connected to the capillary gap and over the opening of the Capillary gap is arranged.
- the overflow vessel is preferably adjustable in height. The height of the overflow vessel is proportional to the media flow through the capillary gap and thus the layer thickness.
- the coating module two parallel plates and one arranged between these on, so you can easily How different capillary gaps are generated. This makes possible es, coating media of different viscosity to apply and the variable feed speed of the Different layer thicknesses under the capillary to create.
- the capillary gap mentioned can be simplified Be determined by cutting out the film. The two For example, plates can be screwed together releasably his. Changing the film to change the width of the The capillary gap is then particularly simple.
- the method according to the invention results from the independent Claim 10. It is also essential here that when coating a volume flow through the capillary gap from top to bottom takes place and the substrate with the surface to be coated is led upwards past the capillary gap.
- the device 1 shown in FIG. 1 has a coating module 2, which is attached to a frame 3. Below the Coating module 2, a transport device 19 is arranged, with which a substrate 23 to be coated for coating an upper flat surface 23a preferably horizontally on Coating module 2 is passed.
- the substrate 23 is in particular a plate or disc, for example a glass or Ceramic plate.
- the coating module 2 is via a liquid line 14 connected to an overflow vessel 25 the coating medium 28 the coating module 2 during coating is delivered later.
- the coating module 2 has two plates 4 and 5 arranged parallel to one another, between which a film 6 with a defined thickness is arranged.
- the two plates 4 and 5 are made of glass or metal, for example, and are ground and polished to ensure a corresponding surface quality.
- the film 6 is provided with a cutout 8a which forms a gap 8 which is essentially rectangular and is closed at the side and at the top.
- the gap 8 has an opening 9 which has a rectangular shape and is formed by parallel, comparatively sharp edges 7 of the plates 4 and 5 and lateral edges 6a of the film 6.
- the width A of the capillary gap 8 is in the range from 5 ⁇ m to a few millimeters.
- a capillary gap 8 with a width A of 150 ⁇ m is suitable for applying a 2 ⁇ m thick layer.
- the coating medium 28 is applied at a temperature of approximately 20 ° C. and has a viscosity of approximately 7 mPas -1 .
- the two plates 4 and 5 are with a plurality of fastening screws 33 firmly screwed together.
- the slide 6 is through the screws 33 firmly and liquid-tight between the Plates 4 and 5 fixed.
- the film can be removed and through another film be replaced with another strength.
- By replacing the film 6 can be the width A of the capillary gap in a simple manner 8 can be changed.
- the film 6 is preferably one Plastic or metal foil. Such films can be very small tolerance, for example with a thickness deviation ⁇ 1% getting produced.
- the width A of the capillary gap 8 is thus exactly defined, but can still by exchanging the film 6 can be changed easily.
- a channel 10 is arranged on the inside 5a of the plate 5, which, according to FIG. 2, extends essentially over the entire length of the capillary gap, and which extends in the upper region the capillary gap 8 is located.
- This channel 10 is over a Bore 11 in the plate 5 and via a connection device 12 connected to the liquid line 14.
- a control device 16 is provided, which is connected to the valve 13 via a line 15.
- the valve 13 is preferably pneumatically controlled. However, it is conceivable also a controller with a stepper motor.
- the line 14 is connected to the overflow vessel 25, which via the opening 9 of the capillary gap 8 is arranged.
- the overflow vessel 25 is by means of a suitable adjusting device 34 height-adjustable attached to a support 40.
- the amount of Overflow vessel 25 above opening 9 is in the range of 10 up to 50 cm.
- the pressure of the coating medium 28 in the capillary gap 8 is proportional to the level of the liquid level 29a over the opening 9 of the capillary gap 8.
- the overflow vessel 25 has an outer vessel 26 and an inner one Vessel 27 on.
- the inner vessel 27 is at its lower End connected to the liquid line 14 and has one Overflow edge 29 on which coating medium 28 from the inner vessel 27 can get into the outer vessel 26.
- a Liquid pump 31 delivers via a liquid line 30 Coating medium 28 from a reservoir 32 the overflow vessel 25 to. Excess coating medium 28 becomes via a return line 41 from the overflow vessel 25 to the Reservoir 32 returned.
- the liquid level is 29a so regardless of the height of the overflow vessel 25 and also regardless of the consumption of the coating medium 28 during the Coating kept constant. Accordingly, it is guaranteed that during the coating process the pressure of the Coating medium 28 in the capillary gap 8 is constant.
- the Overflow vessel 25 could also by a screw conveyor or a pressure cylinder to be replaced. It is essential that through this device medium can be supplied with constant pressure can.
- the transport device 19 has an endless conveyor belt 20 on that around a drive roller 21 and a deflection roller 22nd is laid.
- the drive roller 21 is with a drive 18, for example an electric motor driven by a signal line 17 is connected to the controller 16.
- It is here other transport devices are also conceivable, for example a Transport sled, or a transport device with rollers.
- the substrate 23 can on its underside 23b with suitable and Means not shown here, for example by means of a vacuum plate being held.
- the substrate 23 with the transport device 19 from left to right transported.
- the transport is preferably even and can be infinitely adjusted by means of the control 16.
- the Substrate 23 is preferably transported in a horizontal orientation. An inclined orientation is also conceivable. Finally an embodiment is also conceivable in which the substrate 23 is not transported linearly, but is rotated.
- the substrate 23 is coated with the valve closed 13 this with the surface to be coated 23a above the opening 9 out.
- the substrate 23 is at a standstill Valve 13 opened and thus a uniform flow of Coating medium 28 introduced through the capillary gap 8.
- the gap S between the surface 23a and the edges 7 becomes now filled with substrate 23 and the substrate 23 wetted.
- the Transport device 19 activated and the substrate 23 in Figure 7 in the direction of arrow 37 from left to right with constant Speed moves linearly.
- the coating liquid 28 supplied at constant pressure becomes uniform on the substrate 23 Layer 43, as shown in FIG. 7.
- valve 13 is again closed.
- the valve 13 is preferably closed before reaching the end of the substrate, such that when it is reached of the substrate end in the gap S, the supply of coating medium is interrupted and the coating medium does not have the Edge of the substrate end can flow.
- the right time to close is especially the viscosity of the medium 28 dependent and can be optimized in the process.
- the device 1 is now again for another coating ready.
- the applied layer 43 is dried in a known manner.
- the layer thickness after drying is, for example 2.5 to 3 ⁇ m.
- the layer thickness is essentially determined by the viscosity and the solids content of the coating medium 28, as well as the height of the overflow vessel 25 above the opening 9, the width A of the capillary gap 8 and the transport speed of the substrate 23.
- the above-mentioned layer thickness of 2.5 to 3 pm is obtained, for example, with a coating medium 28 which has a solids content of 10% and a viscosity of approximately 5.5 mPas -1 .
- the temperature of the coating medium 28 is 20 ° C. and the height of the overflow vessel 25 above the surface 23a to be coated is 28 mm.
- the deviations in the thickness of the layer 43 are generally less than 1%.
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Coating Apparatus (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Optical Filters (AREA)
Abstract
Description
- Figur 1
- schematisch ein Ansicht einer erfindungsgemässen Vorrichtung,
- Figur 2
- eine Ansicht eines Beschichtungsmoduls,
- Figur 3
- einen Schnitt durch das Beschichtungsmodul entlang der Linie III-III,
- Figur 4
- einen Schnitt durch das Beschichtungsmodul entlang der Linie IV-IV,
- Figur 5
- einen Schnitt durch das Beschichtungsmodul entsprechend Figur 3, jedoch mit gefüllten Kapillarspalt, und
- Figuren 6 und 7
- schematisch das Beschichten eines ebenen Substrates.
Claims (15)
- Vorrichtung zum Beschichten eines ebenen Substrates (23), mit einem einen Kapillarspalt (8) aufweisenden Beschichtungsmodul, welcher Kapillarspalt (8) mit einem flüssigen Beschichtungsmedium (28) gefüllt ist und eine Öffnung (9) aufweist, an welcher eine zu beschichtende Oberfläche (23a) des Substrates (23) in vergleichsweise kleinem Abstand vorbeizuführen ist, so dass sich eine Schicht (43) auf der genannten Oberfläche (23a) abscheidet, dadurch gekennzeichnet, dass der Kapillarspalt (8) unten offen ist und über einen Versorgungsraum (25, 27) mit Beschichtungsmedium (28a) gefüllt wird und das Substrat (23) unter der Öffnung (9) des Kapillarspaltes (8) mit der zu beschichtenden Oberfläche (23a) nach oben vorbeigeführt wird.
- Vorrichtung nach Anspruch 1, gekennzeichnet durch eine Zuführvorrichtung (25), mit welcher dem Kapillarspalt (28) über eine Öffnung (11) des Beschichtungsmoduls (2) Beschichtungsmittel (28) nachlieferbar ist.
- Vorrichtung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass ein Überlaufgefäss (25) vorgesehen ist, das über eine Flüssigkeitsleitung (14) mit dem Kapillarspalt (8) verbunden und über der Öffnung (9) des Kapillarspaltes (8) angeordnet ist.
- Vorrichtung nach Anspruch 3, dadurch gekennzeichnet, dass in der Flüssigkeitsleitung (14) ein Ventil (13) angeordnet ist.
- Vorrichtung nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass das Überlaufgefäss (25) höhenverstellbar ist.
- Vorrichtung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Beschichtungsmodul (2) zwei parallel zueinander angeordnete Platten (4, 5) und eine zwischen diesen Platten angeordnete Folie (6) aufweist.
- Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, dass die Folie (6) auswechselbar ist.
- Vorrichtung nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass die beiden Platten (4, 5) lösbar miteinander verschraubt sind.
- Vorrichtung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Kapillarspalt (8) oben und seitlich geschlossen ist.
- Verfahren zum Beschichten eines Substrates (23) mit einem Beschichtungsmodul (2), an dem das Substrat (23) mit der zu beschichtenden Oberfläche (23a) vorbeigeführt wird und sich hierbei eine Schicht (43) des Beschichtungsmediums (28) auf dieser Oberfläche (23a) abscheidet, wobei während der Beschichtung dem Beschichtungsmodul (2) Beschichtungsmedien (28) nachgeliefert werden, dadurch gekennzeichnet, dass das Substrat (23) mit der zu beschichtenden Oberfläche (23a) nach oben am Beschichtungsmodul (2) vorbeigeführt wird und dass hierbei Beschichtungsmedium (28) von oben nach unten an das Substrat (23) abgegeben wird.
- Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass dem Beschichtungsmodul (2) während des Beschichtens aus einem Vorratsgefäss (25) mittels einer am Beschichtungsmodul (2) angeschlossenen Flüssigkeitsleitung (14) gleichmässig Beschichtungsmedium (28) nachgeliefert wird.
- Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass das Beschichtungsmedium (28) aus einem Vorratsbehälter (32) einem Überlaufgefäss (25) und von diesem dem Beschichtungsmodul (2) zugeführt wird.
- Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass das im Überlaufgefäss (25) überlaufende Beschichtungsmedium (28) in den Vorratsbehälter (32) zurückgeführt wird.
- Verfahren nach einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, dass ein von einer Steuervorrichtung (16) gesteuertes Ventil (13) sowie eine Transportvorrichtung (19) für das Substrat (23) vorgesehen sind und dass die Steuervorrichtung (16) die Transportvorrichtung (19) steuert.
- Verfahren nach einem der Ansprüche 11 bis 14, dadurch gekennzeichnet, dass nach einem Öffnen des Ventils (13) und einer Benützung des stillstehenden Substrates (23) während einer vorbestimmten Zeitspanne das Substrat (23) durch eine Aktivierung der Transportvorrichtung (19) zum Beschichten transportiert wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH249698 | 1998-12-17 | ||
CH249698 | 1998-12-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1010473A2 true EP1010473A2 (de) | 2000-06-21 |
EP1010473A3 EP1010473A3 (de) | 2003-05-28 |
EP1010473B1 EP1010473B1 (de) | 2006-07-12 |
Family
ID=4235122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99811153A Expired - Lifetime EP1010473B1 (de) | 1998-12-17 | 1999-12-13 | Vorrichtung und Verfahren zum Beschichten eines ebenen Substrates |
Country Status (6)
Country | Link |
---|---|
US (1) | US6383571B1 (de) |
EP (1) | EP1010473B1 (de) |
CA (1) | CA2292271C (de) |
DE (1) | DE59913661D1 (de) |
ES (1) | ES2274611T3 (de) |
MX (1) | MXPA99011776A (de) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009172556A (ja) * | 2008-01-28 | 2009-08-06 | Seiko Epson Corp | スリットコート式塗布装置及び塗布方法 |
JP5719546B2 (ja) * | 2009-09-08 | 2015-05-20 | 東京応化工業株式会社 | 塗布装置及び塗布方法 |
US8608525B1 (en) | 2012-06-05 | 2013-12-17 | Guardian Industries Corp. | Coated articles and/or devices with optical out-coupling layer stacks (OCLS), and/or methods of making the same |
US9696012B2 (en) | 2012-10-04 | 2017-07-04 | Guardian Industries Corp. | Embedded LED assembly with optional beam steering optical element, and associated products, and/or methods |
US9651231B2 (en) | 2012-10-04 | 2017-05-16 | Guardian Industries Corp. | Laminated LED array and/or products including the same |
US9956752B2 (en) | 2012-10-04 | 2018-05-01 | Guardian Glass, LLC | Methods of making laminated LED array and/or products including the same |
US9263701B2 (en) | 2013-03-14 | 2016-02-16 | Guardian Industries Corp. | Coated article and/or device with optical out-coupling layer stack (OCLS) including vacuum deposited index match layer over scattering matrix, and/or associated methods |
JP6272138B2 (ja) * | 2014-05-22 | 2018-01-31 | 東京エレクトロン株式会社 | 塗布処理装置 |
CN105080789B (zh) * | 2015-08-10 | 2017-11-07 | 深圳市华星光电技术有限公司 | 涂布装置及涂布器 |
WO2017201108A1 (en) * | 2016-05-18 | 2017-11-23 | San Diego State University Research Foundation | Methods and systems for ballistic manufacturing of micro/nano coatings and artifacts |
CN105964481A (zh) * | 2016-06-11 | 2016-09-28 | 深圳市新嘉拓自动化技术有限公司 | 双模腔模头 |
KR101990704B1 (ko) * | 2017-11-24 | 2019-06-18 | 고려대학교 산학협력단 | 코팅 비드 영역이 개선된 슬롯 코팅 장치 |
CN108107523A (zh) * | 2017-12-29 | 2018-06-01 | 山东太平洋光纤光缆有限公司 | 一种缓冲型紧套光纤润滑层生产装置 |
CN109759282B (zh) * | 2019-03-19 | 2023-06-16 | 宁波甬安光科新材料科技有限公司 | 一种用于连续稳定均匀涂胶的供胶装置及胶液涂布方法 |
DE112020003653T5 (de) * | 2019-07-29 | 2022-04-21 | Xtpl S.A. | Verfahren zum Abgeben einer metallischen Nanopartikelzusammensetzung aus einer Düse auf ein Substrat |
EP3825012A1 (de) * | 2019-11-22 | 2021-05-26 | Bostik Sa | Verwendung einer rohzuschnittplatte zur verhinderung des tropfens in eine düsenschlitzbeschichtung |
CN111229541B (zh) * | 2020-03-17 | 2023-09-22 | 中国工程物理研究院激光聚变研究中心 | 用于单面涂膜的降液式提拉涂膜机 |
CN113210198A (zh) * | 2021-04-27 | 2021-08-06 | 深圳顺络电子股份有限公司 | 一种流延设备 |
CN113893997B (zh) * | 2021-09-26 | 2023-02-10 | 浙江航威专用设备有限公司 | 一种狭缝涂布头 |
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US5650196A (en) | 1993-05-05 | 1997-07-22 | Steag Microtech Gmbh | Device for coating substrates in semiconductor production |
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DE4445985A1 (de) * | 1994-12-22 | 1996-06-27 | Steag Micro Tech Gmbh | Verfahren und Vorrichtung zur Belackung oder Beschichtung eines Substrats |
EP0761317B1 (de) * | 1994-12-28 | 2002-07-10 | Toray Industries, Inc. | Beschichtungsverfahren und -vorrichtung |
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WO1998042451A1 (en) | 1997-03-25 | 1998-10-01 | Tyco Group S.A.R.L. | Dual capillary coating |
-
1999
- 1999-12-13 DE DE59913661T patent/DE59913661D1/de not_active Expired - Lifetime
- 1999-12-13 ES ES99811153T patent/ES2274611T3/es not_active Expired - Lifetime
- 1999-12-13 EP EP99811153A patent/EP1010473B1/de not_active Expired - Lifetime
- 1999-12-15 MX MXPA99011776A patent/MXPA99011776A/es not_active IP Right Cessation
- 1999-12-16 CA CA002292271A patent/CA2292271C/en not_active Expired - Fee Related
- 1999-12-17 US US09/466,584 patent/US6383571B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5650196A (en) | 1993-05-05 | 1997-07-22 | Steag Microtech Gmbh | Device for coating substrates in semiconductor production |
Also Published As
Publication number | Publication date |
---|---|
US6383571B1 (en) | 2002-05-07 |
CA2292271A1 (en) | 2000-06-17 |
DE59913661D1 (de) | 2006-08-24 |
MXPA99011776A (es) | 2005-04-19 |
CA2292271C (en) | 2008-03-18 |
EP1010473A3 (de) | 2003-05-28 |
ES2274611T3 (es) | 2007-05-16 |
EP1010473B1 (de) | 2006-07-12 |
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