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DE1288174B - Metallischer UEberzug auf einer isolierenden Unterlage - Google Patents

Metallischer UEberzug auf einer isolierenden Unterlage

Info

Publication number
DE1288174B
DE1288174B DEI23747A DEI0023747A DE1288174B DE 1288174 B DE1288174 B DE 1288174B DE I23747 A DEI23747 A DE I23747A DE I0023747 A DEI0023747 A DE I0023747A DE 1288174 B DE1288174 B DE 1288174B
Authority
DE
Germany
Prior art keywords
layer
metal
coating
base
evaporation
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.)
Pending
Application number
DEI23747A
Other languages
English (en)
Inventor
Ayling Stanley Gerald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Micronas GmbH
Original Assignee
Deutsche ITT Industries GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB20201/62A external-priority patent/GB1010111A/en
Priority claimed from GB36013/62A external-priority patent/GB1044689A/en
Priority claimed from DEST19973A external-priority patent/DE1179280B/de
Application filed by Deutsche ITT Industries GmbH filed Critical Deutsche ITT Industries GmbH
Publication of DE1288174B publication Critical patent/DE1288174B/de
Pending legal-status Critical Current

Links

Classifications

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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L24/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/40—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal all coatings being metal coatings
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/027—Graded interfaces
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Description

Vakuum aufgedampft werden, und zwar zusammen 15 die einen aus drei Teilschichten 2,3 und 4 bestehenmit einer Haftzwischenschicht, die aus Kupfer den metallischen Überzug trägt. Die Teilschicht 2 ist bestehen kann. Die Schichten können miteinander ein Grundüberzug aus Chrom, die Teilschicht 3 ist legiert werden. eine Mischung aus Chrom und Gold, wobei die
Das Problem der guten Haftbarkeit an einer Mischung derart abgestuft ist, daß der Chromanteil Unterlage ist auch in der deutschen Patentschrift 20 mit dem Abstand der Teilschicht von der Teil-656 875, der deutschen Auslegeschrift 1006 692 und schicht 2 gleichmäßig abnimmt. Die oberste Teilin »Technische Rundschau« vom 30. 3.1961 auf schicht 4 besteht aus Gold.
den S. 33 und 35 behandelt. So schlägt die erst- Die Teilschicht 3 ist so abgestuft, daß der progenannte Patentschrift vor, als gut haftende Schicht zentuale Anteil von Chrom an der Zwischenfläche auf nichtmetallischen Werkstoffen, wie Glas, Por- 25 der Chromteilschicht 2 etwa 100% beträgt und bis zellan oder Emaille, zuerst eine dünne Zwischen- auf 0% an der reinen Goldteilschicht 4 gleichmäßig schicht eines Metalls der Eisengruppe oder von abnimmt.
Chrom, Wolfram oder Molybdän durch Kathoden- F i g. 2 in Form eines Diagramms die Zusammenzerstäubung aufzubringen, während eine zweite Überzug mit dem Abstand von der Unterlage 1 sich Schicht aus Silber oder Nickel besteht. Dieses Ver- 30 ändert. Die Symbole 1/2, 2/3,. 3/4 bezeichnen die fahren dient der Herstellung von gut haftenden Berührungsflächen zwischen der Unterlage 1, der Oberflächenspiegelschichten. Die genannte Auslege- Teilschicht 2 usw. Die abgestufte Teilschicht 3 kann schrift verfährt bei der Herstellung von fest haften- natürlich als aus sehr dünnen parallelliegenden den Metallbelegungen, auf Unterlagen aller Art, homogenen Schichten bestehend betrachtet werden, z. B. bei der Herstellung von Kondensatorbelägen 35 wobei jede Schicht einen festen Prozentsatz von und Widerstandsschichten, durch Nacheinander- Chrom enthält, welcher vom Abstand der Zwischenaufdampfen von mindestens zwei legierungsbildenden fläche 2/3 abhängt. (Die Teilschicht 2 besteht voll-Metallen so, daß auf die isolierende Unterlage das ständig aus Chrom, wie oben ausgeführt.) edlere der beiden Metalle aufgedampft wird, wobei Es ist anzunehmen, daß eine derartige Erzeugung
dieses positives Normalpotential besitzen soll, wäh- 40 eines metallischen Überzugs ein Minimum an rend als unedles Metall Cadmium verwendet wird. scharfen Unstetigkeiten im Überzug ergibt und daß Der Aufsatz in »Technische Rundschau« schließlich
beschäftigt sich mit den Eigenschaften und Herstellungsverfahren von Überzügen aus Platinmetallen
(Rhodium, Palladium) für gedruckte Schaltungen. 45
Die Erfindung betrifft somit einen metallischen Überzug auf einer isolierenden Unterlage, wobei der Überzug aus mehreren Teilschichten eines auf der Unterlage gut haftenden Metalls und eines zweiten, weich lötbaren Metalls besteht, wobei sich ferner auf der Unterlage eine Teilschicht des gut haftenden Metalls befindet und die oberste Teilschicht aus dem weich lötbaren Metall besteht und wobei die beiden Metalle natürliche oder absichtlich zugefügte, die
Adhäsion und das Weichlöten aber nicht beeinträch- 55 enthalten, deren eine Seite auf eine Weise, die weiter tigende Verunreinigungen enthalten können. unten beschrieben wird, chemisch gereinigt wurde,
Die bekannten metallischen Überzüge, insbeson- um den Überzug durch Verdampfung zu empfangen, dere die aus zwei Schichten bestehenden, zeigen die Diese Seite ist gegen ein Paar von Gefäßen 6 und 7 Tendenz, unter mechanischer Beanspruchung zu ver- aus Molybdän gerichtet, die chemisch gereinigtes sagen. Die Erfindung bezweckt daher die Schaffung 60 Chrom bzw. Gold enthalten. Die Gefäße 6 und 7 einer Zusammensetzung, in welcher die mechanische befinden sich in thermischem Kontakt mit den jewei-Festigkeit des abgelagerten Überzugs größer ist als ligen Heizwicklungen 8 und 9, die von einer Strombei den bekannten Überzügen. Diese Aufgabe wird quelle über getrennt steuerbare variable Widerstände erfindungsgemäß dadurch gelöst, daß der prozentuale 10,10 a gespeist werden. Der bei 11 gezeigte Mittel-Anteil des gut haftenden Metalls von Schicht zu 65 schirm gestattet, die Metalldämpfe erst kurz vor der Schicht bis zur obersten Teilschicht kontinuierlich Ablagerung auf der Unterlage zu mischen. Weitere oder stufenweise abnimmt. Führungsmittel können vorgesehen werden, um die
Nachfolgend wird die Erfindung sowie ein Ver- Dämpfe in das Mischungsgebiet zu führen.
die Anwesenheit solcher Unstetigkeiten den Überzug gegenüber mechanischen Spannungen empfindlicher machen würde.
Chrom wurde im vorliegenden Beispiel als erste Teilschicht gewählt, weil es gute Adhäsionseigenschaft an Glas aufweist, während Gold für die oberste Teilschicht verwendet wurde, da es weich lötbar ist und an Luft nicht oxydiert.
Die Erzeugung des metallischen Überzugs der Fig. 1 wird jetzt unter Bezugnahme auf Fig. 3 beschrieben, in welcher Stützen, Klammern usw. zwecks Vereinfachung weggelassen sind. In einer Glasglocke 5 ist eine hängende Glasunterlage 1
Die vorbereitete Seite der Unterlage 1 ist durch eine Platte 12, die in diesem Ausführungsbeispiel aus rostfreiem Stahl besteht, zum Teil abgeschirmt. Diese Platte weist eine Öffnung auf, um den Dämpfen zu gestatten, den Teil der Unterlage zu erreichen, auf dem der Überzug abzulagern ist. Die Öffnung in der Platte 12 wird mittels eines Photoätzverfahrens hergestellt. Eine verstellbare Aluminiumabschlußklappe 13 ist vorgesehen, um eine Ablagerung der Dämpfe zu verhindern, wenn die Gefäße 6 und 7 heiß sind, jedoch keine Ablagerung erwünscht ist. Die Abschlußklappe 13 wird von außen magnetisch bewegt.
Die Heizwicklungen sind von Strahlungsschirmen umhüllt (nicht gezeigt), um die unnötige Heizung von Nachbarteilen und dadurch ihre unnötige Entgasung zu vermindern. Aus demselben Grund sind die Wicklungen 8 und 9 um ungefähr 12,7 mm von der Grundplatte entfernt.
Im Betrieb wird der Druck innerhalb der Glocke 5 unter 0,0002 mm Hg gehalten, und das mit Chrom gefüllte Gefäß 6 wird während 30 Sekunden bei geschlossener Klappe 13 auf 1880° C vorgeheizt. Die Klappe 13 wird dann geöffnet, um die Unterlage frei zu machen, und die Ablagerung wird gemäß der folgenden Tabelle ausgeführt:
Überzüge, die, wie oben beschrieben, abgelagert werden, widerstandsfähig sind, wenn sie auf Glas oder wärmehärtenden Stoffen abgelagert werden und auch wenn der Überzug einen aufgebrachten Aluminiumüberzug überdeckt, welcher eine Elektrode eines Aluminium-Quarz-Aluminium-Flächenkondensators bildet. Als versucht wurde, mit einem Aluminium-Gold-Überzug eine Verbindung mit einem solchen Kondensator zu machen, wurde festgestellt, daß die Aluminium-Aluminium-Bindung nicht so widerstandsfähig war, wie es erwünscht gewesen wäre. Obwohl es sich mit dem Glas gut verbindet, scheint das Aluminium ungeeignet zu sein, sich mit sich selbst zu verbinden.
Die gestrichelte Linie 14 in der F i g. 2 zeigt an, daß die Zusammensetzung der Teilschicht 3 nicht notwendigerweise sich gleichmäßig ändern muß, sondern daß sie aus einer Anzahl diskreter Schichten bestehen kann.
ao Wie oben angedeutet, ist der Vorteil der Erfindung darin zu sehen, daß durch den kontinuierlichen oder abgestuften Übergang des gut haftenden Metalls in das weich lötbare Metall die mechanische Festigkeit des Überzugs wesentlich verbessert wird, so daß das Abheben der Teilschichten oder das Ablösen des gesamten Überzugs von der Unterlage vermieden wird.
Temperatur Temperatur 7pft
der Chromquelle
in 0C		 der Goldquelle
in 0C		 in Sekunden
1880 _ 120
2100 — 60
2100 1310 180
2100 1520 30
2100 Abschalten nach 1520 180
30 Sekunden
30
35
Die Temperaturen wurden mit einem optischen
40
Pyrometer gemessen und sind auf mindestens ± 50° reproduzierbar. Diese Ablesungen sind als Beispiel gegeben, und es kann von diesen abgewichen werden, ohne den resultierenden Überzug zu beeinflussen.
Nach Abschluß der Ablagerung sind, bevor das Vakuum aufgehoben wird, 10 Minuten Abkühlungszeit erforderlich.
Der Überzug ist jetzt im wesentlichen so, wie er oben beschrieben und in F i g. 1 dargestellt ist. Er ist nun lötbar. Es wurde gefunden, daß bei einem Chrom-Gold-Überzug kein Ausglühen nötig ist. Bei einigen anderen Metallpaaren, wie Chrom—Kupfer, ist ein Ausglühen nötig, und es soll in einer nicht oxydierenden Atmosphäre durchgeführt werden, sonst würde eine Oxydschicht die Kupferfläche für Lötzwecke ungeeignet machen.
Die Oberfläche der Unterlage wird für das Anbringen des Überzugs durch Spülen in Azeton, durch Rösten in Luft und dann kurz vor der Ablagerung durch eine 20minutige Ionenreinigung bei 50 mA, 1,5 kV und bei einem Druck von 0,015 mm Hg vorbereitet.
Das zu verdampfende Chrom befindet sich im Gefäß 6 in der Form von Spänen. Diese werden zuerst in eine Kohlenstofftetrachlorid- und Azetonlösung getaucht und dann 2 Minuten mit Ultraschall gereinigt. Nachfolgend werden die Späne in Methanol gespült und in Luft bei 100° C getrocknet.
Es hat sich herausgestellt, daß Chrom-Gold-

Claims (10)

Patentansprüche:
1. Metallischer Überzug auf einer isolierenden Unterlage, wobei der Überzug aus mehreren Teilschichten eines auf der Unterlage gut haftenden Metalls und eines zweiten, weich lötbaren Metalls besteht, wobei sich ferner auf der Unterlage eine Teilschicht des gut haftenden Metalls befindet und die oberste Teilschicht aus dem weich lötbaren Metall besteht und wobei die beiden Metalle natürliche oder absichtlich zugefügte, die Adhäsion und das Weichlöten aber nicht beeinträchtigende Verunreinigungen enthalten können, dadurch gekennzeichnet, daß der prozentuale Anteil des gut haftenden Metalls von Schicht zu Schicht bis zur obersten Teilschicht kontinuierlich oder stufenweise abnimmt.
2. Überzug nach Anspruch 1, dadurch gekennzeichnet, daß die abgestufte Schicht eine Anzahl homogener Teilschichten aufweist, deren prozentualer Anteil an haftendem Metall mit zunehmendem Abstand von der Unterlage abnimmt.
3. Überzug nach Anspruch 1 und 2, dadurch gekennzeichnet, daß sich der prozentuale Anteil an haftendem Metall in jeder Teilschicht höchstens um 20% von dem Anteil der darunterliegenden Schicht unterscheidet.
4. Überzug nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die oberste Teilschicht aus weich lötbarem Metall eine definierte Dicke aufweist.
5. Überzug nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Teilschicht aus dem gut haftenden Metall auf der Unterlage eine definierte Dicke aufweist.
6. Überzug nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das haftende Metall aus Chrom und das weich lötbare Metall aus Gold besteht.
7. Verfahren zur Ablagerung eines metallischen Überzugs auf einer isolierenden Unterlage nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das an der Unterlage gut haftende Metall und das weich lötbare Metall gleichzeitig, jedoch getrennt derart verdampft werden, daß die beiden Metalle sich in der Dampfphase mischen können und daß die Verdampfungsgeschwindigkeit des gut haftenden Metalls mit zunehmender Überzugsdicke verringert wird.
8. Verfahren zur Ablagerung eines metallischen Überzugs auf einer Glasunterlage nach Anspruch 7, dadurch gekennzeichnet, daß ein Chromüberzug durch Verdampfung direkt auf der Unterlage abgelagert wird, daß eine abgestufte Schicht von Chrom und Gold durch Verdampfung aus getrennten Verdampfungsquellen auf den Chromüberzug abgelagert wird, wobei
10 die Metalle in der Dampfphase sich mischen können, bevor sie die Unterlage erreichen, und daß die relative Verdampfungsgeschwindigkeit des Chroms bezüglich der des Goldes so vermindert wird, daß schließlich eine dünne Schicht aus reinem Gold an der Oberfläche abgelagert wird.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Chrom für die Verdampfung in Form von Spänen vorbereitet wird, die zuerst in eine Kohlenstofftetrachlorid- und Azetonlösung eingetaucht, mit Ultraschall gereinigt und dann mit Methanol gespült werden.
10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß die Unterlage zuerst mit Azeton gespült, in Luft erhitzt und durch Ionenreinigung unter geringem Druck gereinigt wird.
Hierzu 1 Blatt Zeichnungen
DEI23747A 1962-05-25 1963-05-21 Metallischer UEberzug auf einer isolierenden Unterlage Pending DE1288174B (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB20201/62A GB1010111A (en) 1962-05-25 1962-05-25 Vapour deposition of metallic films
GB36013/62A GB1044689A (en) 1962-09-21 1962-09-21 Improvements in or relating to mountings for semi-conductor devices
GB39650/62A GB1023531A (en) 1962-05-25 1962-10-19 Improvements in or relating to semiconductor devices
DEST19973A DE1179280B (de) 1962-11-09 1962-11-09 Verfahren zur Herstellung von loetfaehigen Kontaktstellen
GB48863/62A GB1024216A (en) 1962-05-25 1962-12-28 Improvements in or relating to circuit modules including semiconductor devices

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DE1963J0024586 Expired DE1302005C2 (de) 1962-05-25 1963-10-18 Verwendung eines metallischen ueberzugs als grossflaechiger anschluss fuer plenare halbleiterbauelemente

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BE (3) BE632739A (de)
CH (3) CH422927A (de)
DE (2) DE1288174B (de)
GB (2) GB1023531A (de)
NL (3) NL299522A (de)
SE (1) SE316221B (de)

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DE2810523A1 (de) * 1977-03-18 1978-09-21 Nippon Mining Co Leiterplatten fuer gedruckte schaltkreise und verfahren zu ihrer herstellung

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US3361592A (en) * 1964-03-16 1968-01-02 Hughes Aircraft Co Semiconductor device manufacture
US3325702A (en) * 1964-04-21 1967-06-13 Texas Instruments Inc High temperature electrical contacts for silicon devices
GB1052135A (de) * 1964-11-09
US3477123A (en) * 1965-12-21 1969-11-11 Ibm Masking technique for area reduction of planar transistors
DE1283970B (de) * 1966-03-19 1968-11-28 Siemens Ag Metallischer Kontakt an einem Halbleiterbauelement
US3504430A (en) * 1966-06-27 1970-04-07 Hitachi Ltd Method of making semiconductor devices having insulating films
US3840982A (en) * 1966-12-28 1974-10-15 Westinghouse Electric Corp Contacts for semiconductor devices, particularly integrated circuits, and methods of making the same
US3480841A (en) * 1967-01-13 1969-11-25 Ibm Solderable backside ohmic contact metal system for semiconductor devices and fabrication process therefor
US3460003A (en) * 1967-01-30 1969-08-05 Corning Glass Works Metallized semiconductor device with fired-on glaze consisting of 25-35% pbo,10-15% b2o3,5-10% al2o3,and the balance sio2
GB1258580A (de) * 1967-12-28 1971-12-30
DE1789062C3 (de) * 1968-09-30 1978-11-30 Siemens Ag, 1000 Berlin Und 8000 Muenchen Verfahren zum Herstellen von Metallkontaktschichten für Halbleiteranordnungen
US3704166A (en) * 1969-06-30 1972-11-28 Ibm Method for improving adhesion between conductive layers and dielectrics
FR2048036B1 (de) * 1969-06-30 1974-10-31 Ibm
FR2547112B1 (fr) * 1983-06-03 1986-11-21 Thomson Csf Procede de realisation d'un circuit hybride et circuit hybride logique ou analogique
FR2986372B1 (fr) 2012-01-31 2014-02-28 Commissariat Energie Atomique Procede d'assemblage d'un element a puce micro-electronique sur un element filaire, installation permettant de realiser l'assemblage
KR102073790B1 (ko) * 2013-12-09 2020-02-05 삼성전자주식회사 투과형 광 셔터 및 상기 투과형 광 셔터의 제조 방법

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DE1006692B (de) * 1953-10-29 1957-04-18 Siemens Ag Verfahren zur Herstellung festhaftender Metallbelegungen auf Unterlagen aller Art
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DE1006692B (de) * 1953-10-29 1957-04-18 Siemens Ag Verfahren zur Herstellung festhaftender Metallbelegungen auf Unterlagen aller Art
GB874965A (en) * 1958-07-09 1961-08-16 G V Planer Ltd Improvements in or relating to electrical circuits or circuit elements

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DE2810523A1 (de) * 1977-03-18 1978-09-21 Nippon Mining Co Leiterplatten fuer gedruckte schaltkreise und verfahren zu ihrer herstellung

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US3270256A (en) 1966-08-30
CH424889A (de) 1966-11-30
NL299522A (de) 1900-01-01
GB1023531A (en) 1966-03-23
BE637621A (de) 1900-01-01
NL298258A (de) 1900-01-01
BE639640A (de) 1900-01-01
GB1024216A (en) 1966-03-30
DE1302005B (de) 1975-08-07
BE632739A (de) 1900-01-01
CH468719A (de) 1969-02-15
DE1302005C2 (de) 1975-08-07
CH422927A (de) 1966-10-31
SE316221B (de) 1969-10-20
NL292995A (de) 1900-01-01

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