Germanosiloxane materials and optical components comprising...

Details Germanosiloxane materials and optical components comprising... Germanosiloxane materials and optical components comprising...

1998-10-01

2001-06-19

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From heavy metal or aluminum reactant having at least one...

C528S395000, C528S481000, C528S482000, C427S374700, C428S336000

Reexamination Certificate

active

06248852

ABSTRACT:

FIELD OF THE INVENTION
This invention pertains to the field of optical devices and will be described with specific references thereto. However, it will be appreciated that the invention has broader applications and may be advantageously employed in other environments and applications.
BACKGROUND OF THE INVENTION
The present invention relates to the formation of novel germanosiloxane compounds which can be used as spin-on-glass precursors, optically useful films, and precursors to other germania- and silica- based glass objects. It also relates to a method of forming these objects, including germania-silica based glass films, microlenses, lasers, adhesive layers and other glass objects.
Generally, germanium-oxygen bond containing compounds or germoxanes are synthesized through hydrolysis of germanium halides. Since the germanium-oxygen bond is relatively weak and quite subject to hydrolysis by water, the synthesis of certain polygermoxane compounds has to be carried out under non-aqueous conditions. Recently, certain polygermoxanes with formula (R
1
R
2
GeO)
n
(n=3-50) were synthesized through reaction between a germanium hydrocarbyl dihalide and a hydrocarbyllithium [U.S. Pat. No. 5,391,792]. Polygermoxanes with formula (RGeO
1.5
)
n
also were synthesized through the photooxidation of polygermynes [W. J. Szymanski, G. T. Visscher, and P. A. Bianconi,
Macromolecules
, 26, 869(1993)].
Small germoxane compounds have been synthesized through different methods [M. P. Brown and E. G. Rochow,
J. Am. Chem. Soc
., 82, 4166(1960); H. Puff, S. Franken, W. Schuh, and W. Schwab,
J. Organometal Chem
., 254, 31(1983); L. Ro&bgr; and M. Dräger,
Z. Naturforsch
, 39b, 868(1984); S. Masamune, S. Batcheller, J. Park, W. M. Davis, O. Yamashita, Y. Ohta, and Y. Kabe,
J. Am. Chem. Soc
., 111, 1889(1989)]. Small germanosiloxane compounds with one or more Ge—O—Si bond have been synthesized [F. Glockling,
The Chemistry of Germanium
, Academic Press, London(1969); M. Lesbre, P. Mazerolles, and J. Satge,
The Organic Compounds of Germanium
, John Wiley & Sons, London(1971)]. Other germanosiloxane ring compounds were also synthesized through the reaction of diallylsilanediols and germanium halides [H. Puff, M. Bockmann, T. Kok, and W. Schuh,
J. Organometal. Chem
., 268, 197(1984); M. Akkurt, T. R. Kok, P. Faleschini, L. Randaccio, H. Puff, W. Schuh,
J. Organometal. Chem
., 470, 59(1994)].
However, few types of large polygermanosiloxane compounds have been synthesized and applied to the formation of optical materials. It is an object of this invention to provide methods for the synthesis of polygermanosiloxane materials which can be used as germanium-containing Spin-on-Glass (SOG) materials. SOG materials commonly are designed to lead to silica (SiO
2
)like characteristics and fall into two categories called p-SOG and s-SOG. Both are based on organosiloxane molecules. Those that are polymeric with inert organic side chains, such as —CH
3
, —C
2
H
5
, —C
6
H
5
, etc. are called p-SOG. Those with reactive side chains, such as —OH, —OCH
3
, —OC
2
H
5
, —O
2
CH
3
, etc., which are capable of reacting with the other molecules to form polymerized SiO
2
— like materials are called s-SOG. S. Ito, Y. Homma, E. Sasaki, S. Uchimura and H. Morishima,
J. Electrochemical Society
, Vol. 137, No 4, pp 1212-1218, 1990. However, analogous spin-on-glass materials based on organogermanosiloxanes are less common or not available. It is the object of this invention to introduce germanium into polysiloxanes to form germanium-containing SOG materials.
Electronic and optical systems often require films and other objects to function as dielectrics, waveguides, lenses, filters, lasers and other structures. Commonly they are made of silica-like materials that are formed from organosiloxane or other spin-on-glasses or precursors. The optical and electrical properties of silicas formed this way tend to fall in a limited range near those of amorphous SiO
2
itself. For some purposes, however, it would be advantageous to have analogous glassy materials with a substantially different set of properties, especially higher or lower refractive indices, and varied electrical and optical properties. It also would be valuable to have higher refractive index glasses with incorporated transition metal, lanthanide, actinide or other metal ions. And, it would be valuable to have materials that are chemically suited to interact with germanium-containing substrates including silicon, silica, germanium, and germanium-containing layers. Thus, it is also the object of this invention to provide a method to form germanium dioxide doped silicate glass films and other objects with the types of compositions and on the substrates mentioned above.
These and other objects and features of the invention will be apparent from the following summary and description of the invention and from the claims.
SUMMARY OF THE INVENTION
In accomplishing the foregoing and related objects, the invention provides a method of forming germanium containing polysiloxanes and a method of forming germanium containing silicate films and other objects on substrates such as silicon, silica, oxide glasses and others. Typically, polygermanosiloxanes with Ge—O—Si bond are synthesized from dialkyldicholorosilane and dialkyldichlorogermane in a two-phase reaction system, in which the alkyl groups attached to germanium or silicon are saturated hydrocarbon chain, unsaturated hydrocarbon chain or carboxyl terminated hydrocarbon chain with 1-8 carbons, in which the protons of the carboxyl groups can be replaced by metal ions such as alkali, transition metal, rare earth metal and other metal ions to form metal ion doped polydialkylgermanosiloxanes. Germanium esters of carboxyl-containing polydialkylsiloxanes with Ge—O—C═O bonds also are synthesized from the reaction of dialkylgermanol and carboxyl-containing polydialkylsiloxanes, in which the alkyl groups are saturated hydrocarbon chain or unsaturated hydrocarbon chain with 1-8 carbons. The invention also provides a method of forming germanium dioxide containing silicate films or patterns on silicon, silica and other substrates through thermal oxidation of the germanium-containing polysiloxanes mentioned above, and other oxidation method should also work upon the materials mentioned above to form germanium dioxide containing silicate films or pattern structures on silicon or silica.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to novel polydialkylgermanosiloxanes and a process for making them. More particularly, the present invention relates to carboxyl containing polydialkylgermanosiloxanes, and to the use of them as precursors to form germanium dioxide containing silicate films on silicon, silica or oxide glass substrates, and to the use of their salts as precursors to form metal ion and germanium doped silicate films, and moreover to form metal ion and germanium doped silicate pattern structures on silicon, silica and other oxide glass substrates.
One type of composition prepared by a novel method of this invention can be represented by the following general Formula I:
in which R
1
-R
4
are identical or different alkyl, alkenyl, and functionalized alkyl and alkenyl radicals such as vinyl and cyanoalkyl radicals, including cyanopropyl, and n or m is a positive integer with n+m larger than 3, and n/(n+m) ranging 0.01-0.60.
In this invention, dialkyldichlorogermane is hydrolyzed to dialkylgermanium oxide tetramer according to Brown and Rochow's method [M. P. Brown and E. G. Rochow,
J. Am. Chem. Soc
., 82, 4166(1960)]. The dialkylgermanium oxide tetramer is then hydrolyzed by water to form water solution of dialkylgermanol R
1
R
2
Ge(OH)
2
which then reacts with sodium hydroxide in excess and is believed to form sodium dialkylgermanolate which reacts with dialkyldichlorosilane in petroleum ether to form a polydialkylgernanosiloxane which stays in petroleum ether phase.
One of the attractive features of the invention is that a

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