DE10222964A1 - Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layers - Google Patents
Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layersInfo
- Publication number
- DE10222964A1 DE10222964A1 DE10222964A DE10222964A DE10222964A1 DE 10222964 A1 DE10222964 A1 DE 10222964A1 DE 10222964 A DE10222964 A DE 10222964A DE 10222964 A DE10222964 A DE 10222964A DE 10222964 A1 DE10222964 A1 DE 10222964A1
- Authority
- DE
- Germany
- Prior art keywords
- glass
- substrate side
- substrate
- layer
- glass layer
- 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
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims description 67
- 238000000034 method Methods 0.000 claims description 24
- 239000004033 plastic Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 12
- 238000007740 vapor deposition Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 2
- 239000006223 plastic coating Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 41
- 238000003491 array Methods 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003197 gene knockdown Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
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- 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
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- C03C2214/00—Nature of the non-vitreous component
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Abstract
Description
Die Erfindung bezieht sich auf ein Verfahren zur Gehäusebildung bei elektronischen Bauteilen sowie auf so hermetisch verkapselte elektronische Bauteile, insbesondere Sensoren, integrierte Schaltungen und optoelektronische Bauelemente. The invention relates to a method for Housing formation in electronic components and on so hermetically encapsulated electronic components, in particular Sensors, integrated circuits and optoelectronic Components.
Zur Kapselung von integrierten Schaltungen und optoelektronischen Bauelementen ist es bekannt, ein dünnes Glasplättchen mittels einer organischen Klebeschicht auf das Bauteil zu kleben und so die empfindlichen Halbleiterstrukturen abzudecken und zu schützen. Diese Bauweise hat den Nachteil, dass mit der Zeit Wasser in die organische Klebeschicht eindiffundieren kann, welches dann bis zu den Halbleiterstrukturen gelangen kann und diese beeinträchtigt. Die Klebeschichten können ferner durch UV- Bestrahlung altern, was vor allem für elektrooptische Bauteile schädlich ist. For encapsulating integrated circuits and optoelectronic components, it is known to be a thin Glass plate by means of an organic adhesive layer on the Glue component and so the sensitive Cover and protect semiconductor structures. This Construction has the disadvantage that over time, water gets into the can diffuse organic adhesive layer, which then can get to the semiconductor structures and this impaired. The adhesive layers can also by UV Irradiation ages, especially for electro-optical Components is harmful.
Anstelle organischer Klebemittel ist auch schon niedrig schmelzendes Glaslot als Zwischenschicht verwendet worden, welches aufgesprüht, aufgesputtert bzw. mittels Siebdruck- und Dispensertechnologie aufgetragen worden ist. Die Prozesstemperatur beim Aufschmelzen der Glaslotschicht ist jedoch höher als T = 300°C, so dass temperaturempfindliche Halbleiterstrukturen nicht verkapselt werden können. Instead of organic glue it is already low melting glass solder has been used as an intermediate layer, which is sprayed on, sputtered on or by means of screen printing and dispenser technology has been applied. The Process temperature when melting the glass solder layer is however, higher than T = 300 ° C, making it temperature sensitive Semiconductor structures cannot be encapsulated.
Der Erfindung liegt deshalb die Aufgabe zugrunde, ein Verfahren zur Kapselung von elektronischen Bauteilen anzugeben, mit dem eine weitgehend wasserdiffusionsfeste Kapselung bei mäßigen Temperaturen unterhalb von 300°C, vorzugsweise unterhalb 150°C erzielt werden kann. The invention is therefore based on the object Process for encapsulating electronic components specify with which a largely water diffusion resistant Encapsulation at moderate temperatures below 300 ° C, can preferably be achieved below 150 ° C.
Die gestellte Aufgabe wird aufgrund der Maßnahmen des Anspruches 1 gelöst und durch die weiteren Maßnahmen der abhängigen Ansprüche ausgestaltet und weiterentwickelt. Anspruch 14 betrifft ein erfindungsgemäß hergestelltes elektronisches Bauteil. The task is due to the measures of the Claim 1 solved and by the further measures of dependent claims designed and developed. Claim 14 relates to a manufactured according to the invention electronic component.
Das erfindungsgemäße Verfahren der Kapselung mit Aufdampfglas kann bereits angewendet werden, wenn das elektronische Bauteil noch in der Herstellung begriffen ist. Die Verstärkung des Substrats des elektronischen Bauteils durch die aufgedampfte Glasschicht wird ausgenutzt, das Substrat zu stabilisieren, während auf das Substrat von der nicht eingekapselten Seite her eingewirkt wird. Das ansonsten fertig hergestellte elektronische Bauteil kann auch von der Anschlußseite her - unter Freilassung der Anschlüsse - eingekapselt werden. The encapsulation method with vapor deposition glass according to the invention can already be applied if the electronic Component is still in production. The Reinforcement of the substrate of the electronic component the evaporated glass layer is used, the substrate too stabilize while on the substrate from the not encapsulated side is acted on. Otherwise Finished electronic component can also be made by the Connection side - leaving the connections free - be encapsulated.
Je nach den Anforderungen kann die Dicke der aufgedampften Glasschicht 1 bis 1000 µm betragen. Wenn es nur auf hermetischen Abschluss des zu schützenden Bauteils ankommt, liegt die bevorzugte Glasschichtdicke im Bereich zwischen 1 und 50 µm. Für stärkere Belastungen wird die Glasschichtdicke entsprechend dicker gewählt, wobei ein bevorzugter Bereich der Glasschichtdicke zwischen 50 und 200 µm liegt. Ein Aufbau von Mehrfachschichten auch in Kombination mit anderen Materialien ist ebenso möglich. Es ist auch möglich, die Glasschicht mit einer aufgebrachten Kunststoffschicht zu kombinieren, um zu einer strukturellen Verstärkung des elektronischen Bauteils zu gelangen. Depending on the requirements, the thickness of the evaporated Glass layer be 1 to 1000 microns. If only it was on the hermetic seal of the component to be protected arrives, the preferred glass layer thickness lies in the range between 1 and 50 µm. For higher loads, the Glass layer thickness chosen accordingly thicker, with a preferred range of the glass layer thickness between 50 and 200 microns. A structure of multiple layers also in Combination with other materials is also possible. It it is also possible to apply the glass layer with an applied Combine plastic layer to create a structural To gain reinforcement of the electronic component.
Es gibt verschiedene Möglichkeiten, Glas aufzudampfen. Bevorzugt wird die Erzeugung des Glasdampfes mittels Elektronenstrahl aus einem Glasvorrats-Target. Es können Aufdampfraten von mehr als 4 µm/min. erzeugt werden und das hergestellte Glas scheidet sich mit festem Verbund auf der Oberfläche des Substrats ab, ohne dass es eines erhöhten H2O- Gehalt zwecks Bindungswirkung bedarf wie bei niedrig schmelzendem Glaslot. Als Aufdampfglas wird ein Borosilikatglas mit Anteilen von Aluminiumoxid und Alkalioxid bevorzugt, wie es das Aufdampfglas vom Typ 8329 der Firma Schott Glas darstellt. Dieses Glas hat außerdem einen Wärmeausdehnungskoeffizienten, der dem des Substrats von üblichen Halbleiterstrukturen nahekommt, bzw. durch entsprechende Abwandlung in den Komponenten an den Wärmeausdehnungskoeffizienten des Substrats angepasst werden kann. Es kann Aufdampfglas anderer Zusammensetzung verwendet werden, insbesondere in mehreren Schichten übereinander, wobei die Gläser unterschiedliche Eigenschaften hinsichtlich Brechungsindex, Dichte, Härte usw. besitzen können. There are various ways of vapor deposition on glass. The generation of the glass vapor by means of an electron beam from a glass stock target is preferred. Evaporation rates of more than 4 µm / min. are produced and the glass produced is deposited with a firm bond on the surface of the substrate without requiring an increased H 2 O content for the binding effect, as in the case of low-melting glass solder. A borosilicate glass with proportions of aluminum oxide and alkali oxide is preferred as the vapor deposition glass, as is represented by the type 8329 vapor deposition glass from Schott Glas. This glass also has a coefficient of thermal expansion that approximates that of the substrate of conventional semiconductor structures, or can be adapted to the coefficient of thermal expansion of the substrate by appropriate modification in the components. Evaporating glass of a different composition can be used, in particular in several layers one above the other, the glasses having different properties in terms of refractive index, density, hardness, etc.
Weiterhin kann durch geeignete Materialkombination das Aufbringen einer Mischschicht aus anorganischen und organischen Bestandteilen realisiert werden. Diese Mischschicht ist durch eine Verringerung der Sprödigkeit gekennzeichnet. Furthermore, by using a suitable combination of materials Application of a mixed layer of inorganic and organic components can be realized. This Mixed layer is due to a reduction in brittleness characterized.
Wenn die Glasschicht auf einer ersten Seite des Substrats des elektronischen Bauteils aufgebracht wird, während dieses elektronische Bauteil noch nicht fertig hergestellt ist, kann es zur Handhabung bei dieser Fertigherstellung zweckmäßig sein, eine das Bauteil verstärkende Kunststoffschicht über der Glasschicht anzubringen. In diesem Fall wird die Glasschicht in einer Dicke erzeugt, die für die Abkapselung bzw. den hermetischen Abschluss gegenüber eindringenden diffundierenden Stoffen genügt, während die Kunststoffschicht in einer Dicke erzeugt wird, wie sie für die Stabilisierung bei der Weiterverarbeitung des Bauteils benötigt wird. If the glass layer on a first side of the substrate of the electronic component is applied during this electronic component is not yet finished, can it is useful for handling this finished production be a plastic layer reinforcing the component to attach the glass layer. In this case the Glass layer in a thickness created for the encapsulation or the hermetic seal against penetrating Diffusing substances suffice while the plastic layer is produced in a thickness as used for stabilization is required for further processing of the component.
In einem solchen Fall kann Material von der zweiten nicht gekapselten Substratseite abgetragen werden, so dass Anschlüsse an das Bauteil hergestellt werden können, die von der Unterseite in das Bauteil hineinreichen und somit durch das Bauteil selbst geschützt sind, wenn dieses endgültig von seinem Einsatzort eingebaut wird. Dies ist vor allem im Falle von Sensoren bedeutsam. In such a case, material from the second cannot encapsulated substrate side are removed so that Connections to the component can be made by reach the bottom into the component and thus through the component itself is protected if it is finally protected by where it is installed. This is especially the case of sensors significant.
Die Erfindung wird anhand der Zeichnung beschrieben. The invention is described with reference to the drawing.
Dabei zeigt: It shows:
Fig. 1 einen Abschnitt eines Wafers mit einer aufgedampften Glasschicht, Fig. 1 shows a portion of a wafer having a vapor-deposited glass layer,
Fig. 2 einen Waferabschnitt mit Glas und Kunststoffschicht, Fig. 2 shows a wafer section with glass and plastic layer,
Fig. 3 die Herstellung von Anschlüssen an den Wafer, Fig. 3 shows the manufacture of terminals on the wafer,
Fig. 4 die zusätzliche Kunststoff-Passivierung der Waferunterseite, Fig. 4, the additional plastic passivation of the wafer underside,
Fig. 5 die Beschichtung der Waferunterseite mit Aufdampfglas, Fig. 5 the coating of the wafer underside with evaporation-coating,
Fig. 6 das Anbringen eines Ball Grid Arrays an den Wafer gemäß Fig. 5, Fig. 6 shows the attachment of a ball grid arrays on the wafer of FIG. 5,
Fig. 7 eine weitere Anbringungsart des Ball Grid Arrays, Fig. 7 shows another method of attachment of the ball grid arrays,
Fig. 8 die Kapselung der Unterseite eines Wafers, Fig. 8, the encapsulation of the underside of a wafer,
Fig. 9 das Anbringen der Ball Grid Arrays am Wafer der Fig. 8, sowie Fig. 9, the mounting of the ball grid arrays on the wafer of FIG. 8, and
Fig. 10 ein Schema einer Verdampfungsanordnung. Fig. 10 is a schematic of an evaporation arrangement.
Fig. 10 zeigt die Anordnung eines Substrats 1 zu einer Aufdampfglasquelle 20. Diese besteht aus einem Elektronenstrahlerzeuger 21, einer Strahlumlenkeinrichtung 22 und einem Glastarget 23, das von einem Elektronenstrahl 24 getroffen wird. An der Auftreffstelle des Elektronenstrahls verdampft das Glas und schlägt sich an der ersten Seite 1a des Substrats 1 nieder. Um das Glas des Targets 23 möglichst gleichmäßig verdampfen zu lassen, wird das Target gedreht und der Strahl 24 gewobbelt. Fig. 10 shows the arrangement of a substrate 1 to a Aufdampfglasquelle 20th This consists of an electron beam generator 21 , a beam deflection device 22 and a glass target 23 which is hit by an electron beam 24 . The glass evaporates at the point of impact of the electron beam and is deposited on the first side 1 a of the substrate 1 . In order to allow the glass of the target 23 to evaporate as evenly as possible, the target is rotated and the beam 24 is wobbled.
Wegen näherer Einzelheiten des möglichen Substrats 1 wird Bezug auf Fig. 1 genommen. Ein Siliziumwafer als das Substrat 1 weist Bereiche 2 mit Halbleiterstrukturen sowie Bereiche 3 mit Anschlußstrukturen auf, die hier als Bond Pad, beispielsweise aus Aluminium, ausgebildet sind. Der Siliziumwafer stellt ein Substrat mit einer Oberflächenrauhigkeit < 5 µm dar. Die Oberseite 1a des Substrats liegt der Unterseite 1b gegenüber. Auf die Oberseite 1a ist eine Glasschicht 4 niedergeschlagen worden, die vorzugsweise aus dem Aufdampfglas des Typs 8329 der Firma Schott gewonnen wurde. Dieser Glastyp kann durch Einwirkung des Elektronenstrahls 24 weitgehend verdampft werden, wobei man in evakuierter Umgebung mit 10-5 mbar Restdruck und einer BIAS Temperatur während der Verdampfung von 100°C arbeitet. Unter diesen Bedingungen wird eine dichte geschlossene Glasschicht 4 erzeugt, die weitgehend gegenüber Gasen und Flüssigkeiten, auch Wasser, dicht ist, jedoch Licht durchlässt, was im Falle von elektrooptischen Bauteilen wichtig ist. For further details of the possible substrate 1 , reference is made to FIG. 1. A silicon wafer as the substrate 1 has regions 2 with semiconductor structures and regions 3 with connection structures, which here are designed as a bond pad, for example made of aluminum. The silicon wafer represents a substrate with a surface roughness <5 microns. The top 1 a of the substrate is opposite the bottom 1 b. A glass layer 4 has been deposited on the top 1 a, which was preferably obtained from the type 8329 vapor-deposition glass from Schott. This type of glass can be largely evaporated by the action of the electron beam 24 , the work being carried out in an evacuated environment with a residual pressure of 10 -5 mbar and a BIAS temperature during the evaporation of 100 ° C. Under these conditions, a dense, closed glass layer 4 is produced, which is largely sealed against gases and liquids, including water, but allows light to pass through, which is important in the case of electro-optical components.
Die Unterseite 1b des Wafers steht für weitere Bearbeitungsschritte zur Verfügung, welche das Nass-, Trocken- und Plasmaätzen bzw. -reinigen umfassen. The underside 1 b of the wafer is available for further processing steps, which include wet, dry and plasma etching or cleaning.
Fig. 2 zeigt eine Deckschicht des Substrats 1, die aus einer Glasschicht 4 und einer Kunststoffschicht 5 besteht. Die Glasschicht 4 hat eine Dicke im Bereich von 1 bis 50 µm, was für die Abkapselung bzw. den hermetischen Abschluss genügt, während die Kunststoffschicht 5 dicker ist, um dem Wafer als Werkstück größere Stabilität für nachfolgende Bearbeitungsschritte zu verleihen. Fig. 2 shows a top layer of the substrate 1 consisting of a glass layer 4 and a plastic layer 5. The glass layer 4 has a thickness in the range from 1 to 50 μm, which is sufficient for the encapsulation or the hermetic seal, while the plastic layer 5 is thicker in order to give the wafer as a workpiece greater stability for subsequent processing steps.
In Fig. 3 ist die weitere Bearbeitung eines Wafers angedeutet. Der Wafer wird an der Unterseite gedünnt und es werden Ätzgruben 6 erzeugt, die bis zu den Bond Pads 3 reichen, welche als Ätzstopp wirken. Die Waferunterseite 1b wird mit einer Kunststofflithographie versehen, wobei die Bereiche mit den Bond Pads 3 offen bleiben. Es werden nunmehr Leitungskontakte 7 auf der Unterseite erzeugt, was beispielsweise durch Besprühen oder Besputtern geschieht, wodurch leitfähige Schichten 7 im Bereich der Ätzgruben 6 erzeugt werden. Nunmehr wird der bei der Lithographie verwendete Kunststoff von der Waferunterseite 1b entfernt. Alsdann wird ein Ball Grid Array 8 an den leitfähigen Schichten 7 angebracht und der Wafer wird entlang von Ebenen 9 aufgetrennt. Es entstehen eine Mehrzahl von elektronischen Bauteilen, deren Halbleiterstrukturen 2 sicher zwischen der Deckschicht 4 und dem Substrat 1 eingebettet und hermetisch verschlossen ist. The further processing of a wafer is indicated in FIG. 3. The underside of the wafer is thinned and etching pits 6 are produced which extend as far as the bond pads 3 , which act as an etching stop. The underside of the wafer 1 b is provided with plastic lithography, the areas with the bond pads 3 remaining open. Line contacts 7 are now produced on the underside, which is done for example by spraying or sputtering, as a result of which conductive layers 7 are produced in the area of the etching pits 6 . Now the plastic used in the lithography is removed from the underside 1 b of the wafer. A ball grid array 8 is then attached to the conductive layers 7 and the wafer is cut along levels 9 . A plurality of electronic components are produced, the semiconductor structures 2 of which are securely embedded between the cover layer 4 and the substrate 1 and hermetically sealed.
Fig. 4 zeigt eine Abwandlung der Ausführungsform der Fig. 3. Es werden die gleichen Verfahrensschritte wie zuvor ausgeführt, jedoch wird der Kunststoff an der Waferunterseite 1b nicht entfernt und bedeckt die Unterseite als Passivierungs- und Schutzschicht 10. FIG. 4 shows a modification of the embodiment in FIG. 3. The same method steps are carried out as before, but the plastic on the underside 1 b of the wafer is not removed and covers the underside as a passivation and protective layer 10 .
Fig. 5 zeigt eine Ausführungsform, bei der anstelle der Kunststoffschicht 10 eine aufgedampfte Glasschicht 11 auf der Unterseite 1b des Substrats aufgebracht werden soll. Wie bei der Ausführungsform der Fig. 3 wird der zur Lithographie verwendete Kunststoff an der Waferunterseite 1b entfernt und die gesamte Waferunterseite 1b wird mit dem Glas bedampft, so dass eine 1 bis 50 µm starke Glasschicht 11 entsteht. Fig. 5 shows an embodiment in which, instead of the plastic layer 10 a vapor-deposited glass layer 11 on the bottom 1 b of the substrate is to be applied. As the plastics on the wafer base 1 used for lithography B is removed in the embodiment of Fig. 3 and the entire wafer bottom side 1 b is vapor-deposited to the glass, so that a 1 is created to 50 microns thick glass layer 11.
Wie bei 11b dargestellt, bedeckt diese Glasschicht auch die nach außen ragenden Teile der Leitungskontakte 7. Zum Anbringen eines Ball Grid Arrays 8 werden diese Bereiche 11b durch Wegschleifen und/oder Wegätzen freigelegt. Danach werden die Ball Grid Arrays angebracht, wie Fig. 6 zeigt, und es erfolgt eine Auftrennung des Wafers zur Bildung einzelner Bauteile, wie bei 9 angedeutet. Die empfindlichen Halbleiterstrukturen 2 sind nach oben und nach unten jeweils durch eine Glasschicht 4 bzw. 11 geschützt. As shown at 11b, this glass layer also covers the outwardly projecting parts of the line contacts 7 . To attach a ball grid array 8 , these areas 11 b are exposed by grinding and / or etching away. The ball grid arrays are then attached, as shown in FIG. 6, and the wafer is separated to form individual components, as indicated at 9. The sensitive semiconductor structures 2 are protected upwards and downwards by a glass layer 4 and 11, respectively.
Bei einer weiteren Ausführungsform der Erfindung wird der Wafer an Trennebenen 9, die nicht durch die Bond Pads verlaufen, aufgetrennt. Dies hat den Vorteil, dass auch ein seitlicher Passivierungsschutz für die Bauteile gewährleistet werden kann. Fig. 7 zeigt ein Beispiel der Auftrennung, bei welchem nur Material der Deckschicht 4 und des Substrats 1 betroffen ist. Es wird zunächst wie bei den zuvor beschriebenen Ausführungsbeispielen vorgegangen, d. h. der Wafer wird von der Unterseite gedünnt und es werden Ätzgruben 6 erzeugt, die bis zur Unterseite der Bond Pads 3 reichen. Die Waferunterseite 1b wird lithographiert, wobei die Bond Pad-Bereiche offen bleiben. Die Leitungskontakte 7 werden im Bereich der Ätzgruben 6 erzeugt, wobei die Ätzgruben außerdem mit leitfähigem Material 12 gefüllt werden. Hier kommt die galvanische Verstärkung durch Ni(P) in Betracht. Nachdem der Kunststoff an der Waferunterseite wenigstens im Bereich der Kontakte 7 entfernt worden ist, werden die Ball Grid Arrays 8 angebracht. Danach erfolgt die Auftrennung des Wafers entlang von Ebenen 9. Man erhält elektronische Bauteile mit hermetische eingeschlossenen Halbleiterstrukturen 2, wobei je nach Vorgehensweise eine analoge Kunststoffschicht 10 vorhanden ist oder fehlt. In a further embodiment of the invention, the wafer is cut at separation planes 9 that do not run through the bond pads. This has the advantage that lateral passivation protection for the components can also be guaranteed. Fig. 7 shows an example of the separation, in which only the material of the cover layer 4 and the substrate 1 is concerned. The procedure is initially the same as in the previously described exemplary embodiments, ie the wafer is thinned from the underside and etching pits 6 are produced which extend to the underside of the bond pads 3 . The underside of the wafer 1 b is lithographed, the bond pad regions remaining open. The line contacts 7 are produced in the area of the etching pits 6 , the etching pits also being filled with conductive material 12 . Here galvanic amplification by Ni (P) comes into consideration. After the plastic on the underside of the wafer has been removed at least in the area of the contacts 7 , the ball grid arrays 8 are attached. The wafer is then separated along levels 9 . Electronic components with hermetically enclosed semiconductor structures 2 are obtained , an analog plastic layer 10 being present or missing, depending on the procedure.
Fig. 8 und 9 zeigen ein Ausführungsbeispiel mit der Erzeugung einer unterseitigen Glasschicht 11. Es wird analog zur Ausführungsform der Fig. 5 in Verbindung mit Fig. 7 vorgegangen, d. h. es werden gefüllte Bond Pads erzeugt und die gesamte Unterseite 1b des Wafers wird mit der Glasschicht 11 beschichtet, die anschließend im Bereich der Ätzgruben 6 entfernt wird, um darauf die Ball Grid Arrays anzubringen, wie in Fig. 9 dargestellt. Nach Auftrennung entlang der Ebenen 9 werden Bauteile mit gekapselten Halbleiterstrukturen 2 erzielt. FIGS. 8 and 9 show an embodiment with the generation of a bottom side glass layer 11. The procedure is analogous to the embodiment of FIG. 5 in connection with FIG. 7, that it filled Bond pads are generated and the entire lower surface 1 b of the wafer is coated with the glass layer 11, which is subsequently removed in the etch pits 6 to then attach the ball grid arrays as shown in Fig. 9. After separation along the levels 9 , components with encapsulated semiconductor structures 2 are achieved.
Das Glassystem der Schicht 4 bzw. 11 sollte wenigstens ein binäres System darstellen. Bevorzugt werden Mehrkomponentensysteme. The glass system of layers 4 and 11 should represent at least one binary system. Multi-component systems are preferred.
Als besonders geeignet hat sich das Aufdampfglas Typ 8329 der
Firma Schott erwiesen, welches folgende Zusammensetzung in
Gewichtsprozent aufweist:
The type 8329 vapor-deposition glass from Schott, which has the following composition in percent by weight, has proven particularly suitable:
Der elektrische Widerstand beträgt ungefähr 1010 Ω/cm
(bei 100°C),
der Brechungsindex etwa 1,470,
die Dielektrizitätskonstante ε etwa 4,8 (bei 25°C, 1 MHz)
tgδ etwa 80 × 10-4 (bei 25°C, 1 MHz).
The electrical resistance is approximately 10 10 Ω / cm (at 100 ° C),
the refractive index is about 1.470,
the dielectric constant ε about 4.8 (at 25 ° C, 1 MHz) tgδ about 80 × 10 -4 (at 25 ° C, 1 MHz).
Zur Erzielung besonderer Eigenschaften der Bauteile kann es zweckmäßig sein, Gläser unterschiedlicher Glaszusammensetzungen für die Glasschichten der Oberseite und der Unterseite zu verwenden. Es ist auch möglich, mehrere Gläser mit unterschiedlichen Eigenschaften, z. B. hinsichtlich Brechungsindex, Dichte, Knoophärte, Dielektrizitätskonstante, tanδ nacheinander auf das Substrat aufzudampfen. It can be used to achieve special properties of the components be appropriate, glasses different Glass compositions for the glass layers of the top and the bottom to use. It is also possible to have several Glasses with different properties, e.g. B. regarding Refractive index, density, Knoop hardness, dielectric constant, evaporate tanδ one after the other onto the substrate.
Anstelle der Elektronenstrahlverdampfung können auch andere Mittel zur Überführung von Materialien, die sich als Glas niederschlagen, angewendet werden. Das Verdampfungsmaterial kann sich beispielsweise in einem Tiegel befinden, der durch eine Elektronenstoßheizung aufgeheizt wird. Eine solche Elektronenstoßheizung beruht auf der Emission von Glühelektronen, die auf den Tiegel hin beschleunigt werden, um mit vorbestimmter kinetischer Energie auf das zu verdampfende Material aufzutreffen. Auch mit diesen Verfahren lassen sich Glasschichten erzeugen, ohne das Substrat, auf dem sich das Glas niederschlägt, allzu stark thermisch zu belasten. Instead of electron beam evaporation, others can Means for transferring materials that are called glass knock down, be applied. The evaporation material can be in a crucible, for example an electron pulse heater is heated. Such Electron impulse heating is based on the emission of Glow electrons that are accelerated towards the crucible, to move towards it with predetermined kinetic energy evaporating material. Even with these procedures layers of glass can be created without the substrate to which the glass condenses, too strongly thermally strain.
Claims (15)
Bereitstellen eines Substrats (1), das einen oder mehrere Bereiche zur Bildung von Halbleiterstrukturen (2) sowie von Anschlussstrukturen (3) aufweist, wobei wenigstens eine erste Substratseite (1a) zu verkapseln ist;
Bereitstellen einer Aufdampfglasquelle (20), die wenigstens ein binäres Glassystem erzeugt;
Anordnen der ersten Substratseite (1a) relativ zur Aufdampfglasquelle derart, dass die erste Substratseite (1a) bedampft werden kann;
Betrieb der Aufdampfglasquelle (20) solange, bis die erste Substratseite (1a) eine Glasschicht (4) trägt, welche eine Dicke im Bereich von 1 bis 1000 µm aufweist. 1. Method for forming housings in electronic components, in particular sensors, integrated circuits and optoelectronic components; with the following steps:
Providing a substrate ( 1 ) which has one or more regions for forming semiconductor structures ( 2 ) and connection structures ( 3 ), at least one first substrate side ( 1 a) being encapsulated;
Providing a vapor deposition glass source ( 20 ) that generates at least one binary glass system;
Arranging the first substrate side ( 1 a) relative to the vapor deposition glass source in such a way that the first substrate side ( 1 a) can be vapor-deposited;
Operation of the vapor deposition glass source ( 20 ) until the first substrate side ( 1 a) carries a glass layer ( 4 ) which has a thickness in the range from 1 to 1000 μm.
die zweite, der ersten Substratseite (1a) gegenüberliegende Substratseite (1b) gedünnt wird,
an der zweiten Substratseite (1b) im Bereich der herzustellenden Anschlussstrukturen Gruben (6) geätzt werden,
die Bereiche zur Bildung der Halbleiterstrukturen (2) unter Verwendung von Kunststoffschichten lithographiert werden,
auf der zweiten Substratseite (1b) in den Bereichen mit Bond Pad-Strukturen (3) Leitungskontakte (7) hergestellt werden,
der Kunststoff von der zweiten Substratseite (1b) entfernt wird,
ein Ball Grid Array (8) an den Leitungskontakten (7) aufgebracht wird, und
der Wafer zur Bildung mehrerer elektronischer Bauteile aufgetrennt wird, die jeweils erste, verkapselte Seiten (1a) aufweisen. 11. The method according to any one of claims 1 to 10, characterized in that the substrate ( 1 ) has a wafer with a plurality of semiconductor structures ( 2 ) and bond pad structures ( 3 ), wherein
the second substrate side ( 1 b) opposite the first substrate side ( 1 a) is thinned,
pits ( 6 ) are etched on the second substrate side ( 1 b) in the region of the connection structures to be produced,
the areas for forming the semiconductor structures ( 2 ) are lithographed using plastic layers,
line contacts ( 7 ) are produced on the second substrate side ( 1 b) in the areas with bond pad structures ( 3 ),
the plastic is removed from the second substrate side ( 1 b),
a ball grid array ( 8 ) is applied to the line contacts ( 7 ), and
the wafer is separated to form a plurality of electronic components, each of which has first, encapsulated sides (1a).
dass nach Entfernung des Kunststoffes von der zweiten Substratseite (1b) die zweite Substratseite insgesamt mit einer Glasschicht (11) im Bereich von 1 bis 50 µm Dicke bedampft wird, und
dass die Leitungskontakte (7) durch örtliche Beseitigung der Glasschicht (11) freigelegt werden, wonach die Schritte des Aufbringens des Ball Grid Arrays (8) und des Auftrennens erfolgen, um beidseitig verkapselte elektronische Bauteile zu erhalten. 13. The method according to claim 11, characterized in
that after removal of the plastic from the second substrate side ( 1 b), the second substrate side as a whole is vapor-coated with a glass layer ( 11 ) in the range from 1 to 50 μm thick, and
that the line contacts (7) are exposed by local removal of the glass layer (11), which carried out the steps of applying the ball grid array (8) and of separating to obtain both sides of encapsulated electronic components.
Priority Applications (68)
Application Number | Priority Date | Filing Date | Title |
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DE10222609A DE10222609B4 (en) | 2002-04-15 | 2002-05-23 | Process for producing structured layers on substrates and methodically coated substrate |
DE10222964A DE10222964B4 (en) | 2002-04-15 | 2002-05-23 | Process for forming housings in electronic components and hermetically encapsulated electronic components |
DE10222958A DE10222958B4 (en) | 2002-04-15 | 2002-05-23 | Process for producing an organic electro-optical element and organic electro-optical element |
AU2003227626A AU2003227626A1 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
CN038133024A CN1659720A (en) | 2002-04-15 | 2003-04-15 | Hermetic encapsulation of organic electro-optical elements |
PCT/EP2003/003907 WO2003088347A2 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
KR1020047016631A KR100636414B1 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
KR10-2004-7016634A KR20040111528A (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
CA002480691A CA2480691A1 (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
AT03737955T ATE411407T1 (en) | 2002-04-15 | 2003-04-15 | METHOD FOR COATING METAL SURFACES |
PCT/EP2003/003872 WO2003087423A1 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
EP03746297.5A EP1495493B1 (en) | 2002-04-15 | 2003-04-15 | Use of a borosilicateglass layer |
US10/511,315 US7326446B2 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
CA002480854A CA2480854A1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
IL16430403A IL164304A0 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
AU2003233973A AU2003233973A1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
US10/511,334 US7825029B2 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
CNA038085690A CN1647276A (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface as protection for copying process and elements concerned |
CA002480737A CA2480737A1 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
US10/511,557 US7396741B2 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrate and composite element |
EP03725032.1A EP1495491B1 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
JP2003585174A JP2005528782A (en) | 2002-04-15 | 2003-04-15 | Method of connecting board and composite elements |
JP2003584357A JP2005528780A (en) | 2002-04-15 | 2003-04-15 | Method of forming a housing for an electronic component and electronic component sealed thereby |
KR1020047016629A KR100679345B1 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
JP2003585192A JP2005527076A (en) | 2002-04-15 | 2003-04-15 | Hermetic sealing of organic electro-optic elements |
KR1020117025576A KR101178935B1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
AU2003233974A AU2003233974A1 (en) | 2002-04-15 | 2003-04-15 | Hermetic encapsulation of organic electro-optical elements |
CNA038085844A CN1646722A (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
JP2003583927A JP2005527459A (en) | 2002-04-15 | 2003-04-15 | Method for making a product having a structured surface |
AU2003232469A AU2003232469A1 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
US10/511,488 US20060051584A1 (en) | 2002-04-15 | 2003-04-15 | Process for producing a product having a structured surface |
AT03737956T ATE393839T1 (en) | 2002-04-15 | 2003-04-15 | METHOD FOR HOUSING FORMATION FOR ELECTRONIC COMPONENTS AS WELL AS HERMETICALLY ENCAPSULATED ELECTRONIC COMPONENTS |
AU2003250326A AU2003250326A1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a copy protection for an electronic circuit and corresponding component |
CNB03808564XA CN100359653C (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
EP03737955A EP1495153B1 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces |
US10/511,566 US7863200B2 (en) | 2002-04-15 | 2003-04-15 | Process of vapor depositing glass layers for wafer-level hermetic encapsulation of electronic modules |
JP2003584356A JP2006503976A (en) | 2002-04-15 | 2003-04-15 | Method for coating a metal surface and substrate having a coated metal surface |
CNB038085682A CN100397593C (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
US10/511,558 US7495348B2 (en) | 2002-04-15 | 2003-04-15 | Process for producing copy protection for an electronic circuit |
JP2003585179A JP2005528783A (en) | 2002-04-15 | 2003-04-15 | How to create copy protection for electronic circuits |
PCT/EP2003/003883 WO2003088370A2 (en) | 2002-04-15 | 2003-04-15 | Hermetic encapsulation of organic electro-optical elements |
EP03737956A EP1495154B1 (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
EP03727305.9A EP1494965B1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
PCT/EP2003/003884 WO2003088340A2 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
DE50309735T DE50309735D1 (en) | 2002-04-15 | 2003-04-15 | METHOD FOR HOUSING FOR ELECTRONIC COMPONENTS SO AS HERMETICALLY CAPTURED ELECTRONIC COMPONENTS |
CA002479823A CA2479823A1 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
IL16429003A IL164290A0 (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
JP2003585167A JP2005527112A (en) | 2002-04-15 | 2003-04-15 | Method for producing pattern layer on substrate |
CA002480797A CA2480797A1 (en) | 2002-04-15 | 2003-04-15 | Method for producing a copy protection for an electronic circuit and corresponding component |
CNB038085836A CN100387749C (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
IL16417103A IL164171A0 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
CA002485022A CA2485022A1 (en) | 2002-04-15 | 2003-04-15 | Method for connecting substrates and composite element |
PCT/EP2003/003882 WO2003087424A1 (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
EP03746159.7A EP1502293B1 (en) | 2002-04-15 | 2003-04-15 | Method for the production of structured layers on substrates |
TW092108722A TW200407446A (en) | 2002-04-15 | 2003-04-15 | Method for producing patterned layers on substrates |
CNB038085410A CN1329285C (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
PCT/EP2003/003881 WO2003088354A2 (en) | 2002-04-15 | 2003-04-15 | Method for producing a copy protection for an electronic circuit and corresponding component |
DE50310646T DE50310646D1 (en) | 2002-04-15 | 2003-04-15 | METHOD OF COATING METAL SURFACES |
KR1020047016632A KR100789977B1 (en) | 2002-04-15 | 2003-04-15 | A process for producing copy protection, an electronic component with the copy protection, a decryption device comprising the component |
AU2003245876A AU2003245876A1 (en) | 2002-04-15 | 2003-04-15 | Method for forming housings for electronic components and electronic components that are hermetically encapsulated thereby |
KR1020047016642A KR100942038B1 (en) | 2002-04-15 | 2003-04-15 | Organic electro-optical elements and process for producing organic electro-optical elements |
AU2003245875A AU2003245875A1 (en) | 2002-04-15 | 2003-04-15 | Method for coating metal surfaces and substrate having a coated metal surface |
CA002505014A CA2505014A1 (en) | 2002-04-15 | 2003-04-15 | Hermetic encapsulation of organic electro-optical elements |
EP03727306A EP1495501A2 (en) | 2002-04-15 | 2003-04-15 | Hermetic encapsulation of organic electro-optical elements |
KR1020047016630A KR100616126B1 (en) | 2002-04-15 | 2003-04-15 | Method for forming housing for electronic components and electronic components that are hermetically encapsulated thereby |
PCT/EP2003/003873 WO2003086958A2 (en) | 2002-04-15 | 2003-04-15 | Method for producing a product having a structured surface |
IL16430004A IL164300A0 (en) | 2002-04-15 | 2004-09-27 | Method for coating metal surfaces and substrate having a coated metal surface |
IL16430104A IL164301A0 (en) | 2002-04-15 | 2004-09-27 | Method for connecting substrates and composite element |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE20205830.1 | 2002-04-15 | ||
DE20205830 | 2002-04-15 | ||
DE10222964A DE10222964B4 (en) | 2002-04-15 | 2002-05-23 | Process for forming housings in electronic components and hermetically encapsulated electronic components |
Publications (2)
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DE10222964A1 true DE10222964A1 (en) | 2003-11-06 |
DE10222964B4 DE10222964B4 (en) | 2004-07-08 |
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DE10222964A Expired - Lifetime DE10222964B4 (en) | 2002-04-15 | 2002-05-23 | Process for forming housings in electronic components and hermetically encapsulated electronic components |
DE10252787A Withdrawn DE10252787A1 (en) | 2002-04-15 | 2002-11-13 | Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layers |
DE10301559A Ceased DE10301559A1 (en) | 2002-04-15 | 2003-01-16 | Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layers |
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DE10252787A Withdrawn DE10252787A1 (en) | 2002-04-15 | 2002-11-13 | Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layers |
DE10301559A Ceased DE10301559A1 (en) | 2002-04-15 | 2003-01-16 | Organic electro-optical element production method for e.g. LED, has layer with vitreous structure deposited over layer structure comprising organic electro-optical material layer formed between pair of conductive layers |
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DE102004063703A1 (en) * | 2004-12-28 | 2006-07-06 | Schott Ag | Vacuum coating system |
DE102005044522A1 (en) * | 2005-09-16 | 2007-03-22 | Schott Ag | Method for applying a porous glass layer |
US7326446B2 (en) | 2002-04-15 | 2008-02-05 | Schott Ag | Method for coating metal surfaces and substrate having a coated metal surface |
US7396741B2 (en) | 2002-04-15 | 2008-07-08 | Schott Ag | Method for connecting substrate and composite element |
US7825029B2 (en) | 2002-04-15 | 2010-11-02 | Schott Ag | Method for the production of structured layers on substrates |
US8168693B2 (en) | 2010-02-12 | 2012-05-01 | Schott Ag | X-ray opaque barium-free glasses and uses thereof |
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US8268739B2 (en) | 2009-02-13 | 2012-09-18 | Schott Ag | X-ray opaque barium-free glasses and uses thereof |
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Also Published As
Publication number | Publication date |
---|---|
DE10222964B4 (en) | 2004-07-08 |
DE10301559A1 (en) | 2003-10-30 |
DE10252787A1 (en) | 2003-11-06 |
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