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June 5, 1973 D. B. KECK . ET AL 3,737,292

METHOD OF FORMING OPTICAL WAVEGUIDE FIBERS
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Waveguide has been one of the more difficult problems in
METHOD OF FORMING OPTICAL the development of an effective optical communications
System.
WAVEGUIDE FEBERS
Donald B. Keck, Big Flats, Peter C. Schultz, Painted (II) Description of the prior art
Post, and Frank Zimar, Hammondsport, N.Y., assignors 5
to Corning Glass Works, Corning, N.Y. A method heretofore used for producing an optical
Fied Jara. 3, 1972, Ser. No. 2:4,84. fiber is described as follows. A rod of glass possessing
int. C. C03c 25/06 the desired core characteristics was inserted into a tube
U.S. C. 65-3 T Claims
O
of glass possessing the desired cladding chaiacteristics.
The temperature of this combination was her raised
ABSTRACT OF THE DISCLOSURE until the viscosity of the materials was low enough for
A method of forming an optical waveguide by forming drawing. The combination was then drawn until the tube
a first coating of glass having a predetermined index of collapsed around and fused to the inside rod. The re.
refraction on the outside peripheral wall surface of a Sulting combination rod was then further drawn until
substantially cylindrical starter rod or member. There its cross-sectional area was decreased to the desired
after, a second coating of glass is applied to the periph dimensions. During the drawing process, the rod and
eral outside surface of the first coating, Said second coat tube would normally be fed at different speeds to attempt
ing having a preselected index of refraction less than the to produce a fiber with the desired core to cladding diam.
index of refraction of the first coating. The starter rod or 20 eter ratio. This method, however, has been sometimes
unsatisfactory because of the particular difficulty in main
member is removed from the assembly following the taining the core and cladding dimensions. Further “resid
application of either the first or second coating. The
resulting substantially cylindrical hollow assembly is llai Water in ordinarily produced glass causes absorp
heated and drawn to reduce the cross-sectional area and tive attenuation. By residual water in glass is meani
to collapse the first and inner coating of glass to form a 25 that the glass contains a high level of OH radical. An ex
planation of "residual water” may be found in U.S.
fiber having a solid cross-sectional area. The collapsed Pat. No. 3,531,271 to W. H. Dumbaugh, Jr. An addi.
first and inner coating forms the fiber core and the second tional problem is that numerous tiny air bubbles and
coating forms the cladding for the fiber. foreign particles are often trapped at the core and cladding
30 interface and become a source of light scattering centers.
BACKGROUND OF THE INVENTION In addition, the core and cladding materials of any wave
(I) Field of the invention guide must be selected so that there is a precise dif
ference between the two indices of refraction. Glass
Waveguides used in optical communications systems tubes and glass rods which simultaneously have precise
are herein referred to as "optical waveguides' and are differences in their indices of refraction, low OH radical
normally constructed from a transparent dielectric ma content, similar coefficients of expansion and similar
terial such as glass or plastic. viscosities are not readily available. Variations in core di.
It is well known to one skilled in the art that light can ameter or in either index of refraction may significantly
be caused to propagate along a transparent fiber struc affect the transmission characteristics of a waveguide.
ture which has a higher refractive index than its sur 4) Another method of forming an optical waveguide is
roundings. The ordinary use of such optical fibers is to described in U.S. patent application Ser. No. 36,267,
transmit a signal or an image, that is light which has filed May 11, 1970 by D. B. Keck and P. C. Schultz and
been modulated in some form, from one point to another. is assigned to a common assignee. That patent application
To be effective, optical fibers produced for these purposes teaches a method of producing an optical waveguide
must avoid excessive attenuation of the transmitted light wherein a single film of material is applied to the inside
usually resulting from one or more causes Such as scatter surface of a tube with the composite structure thereafter
ing, absorption or the like. Further, to be an effective being heated and drawn to form a waveguide iber.
transmitting media for an optical communications sys
tem, an optical waveguide should not only transmit light SUMMARY OF HE JENAC.
without excessive attenuation, but should allow only pre 50
selected modes of light to propagate along the fiber, and It is an object of the present invention ic provide an
should be constructed to minimize cross-talk from ad optical waveguide and a method to econorinicaiiy pro
jacent waveguides and minimize mode dispersion. ducing it which overcome the heretofore noted iisad
Operational theories and other pertinent information Vantages.
concerning optical waveguides may be found in U.S. Other objects of the present invention are to provide a
Pat. No. 3,157,726 issued to Hicks et al.; in the publica method for producing an optical waveguide that wit: shot
tion entitled “Cylindrical Dielectric Waveguide Mode' cause excessive light absorption losses, that will not cause
by E. Snitzer, Journal of the Optical Society of America, excessive dispersion in the transmitted light, that will min
vol. 51, No. 5, pages 491-498, May 1961; and in “Fiber imize cross-talk between adjacent fibers, that inas a low
Optics Principles and Applications' by N. S. Kapany, 60 OH radical content, that does not have light scattesing
Academic Press (1967). centers at the core and cladding interface, and that has
The propagation of light waves is governed by the an otherwise improved interface.
same laws of physics that govern microwave propagation Broadly, according to this invention an opticai wave
and, therefore, can also be studied in terms of mccles. guide is produced by applying a first coating of material
Since each mode of light traveling along a glass fiber to the outside peripheral surface of a substantially cylin
structure propagates at its own inherent velocity, it can drical glass or other material starting member. Thereafter
be shown that information initially supplied to all moc'2s a Second coating of glass is applied to the peripheral out
will be dispersed after traversing a given length of fiber side surface of the first coating, the second coating having
due to different propagation velocities. If light propa a preselected index of refraction less than the index of
tion along an optical fiber could be restricted to pix 70 refraction of the first coating. The starting rod or nem
selected modes, clearly more effective information trais ber is removed from the assembly following the applica
mission would result. Producing a satisfactory optill tion of either the first or second coating. The resulting
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3,737,292
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substantially cylindrical hollow assembly is then either When coatings 10 and 20 are applied by means of the
maintained at or heated to a temperature at which the flame hydrolysis method, the deposited soot must be
materials have a low enough viscosity for drawing and sintered to provide a uniform and dense material. In ac
is drawn to reduce the diameter thereof until the first and cordance with the present invention, coating 10 may be
inner coating of glass is collapsed, that is the longitudinal sintered and its exterior surface suitably finished before
hole is sealed and a solid rod surrounded by the second coating 20 is applied. In such an embodiment, coating 20
coating of glass is formed. Thereafter, continued drawing would thereafter be sintered before subsequent drawing.
of the composite structure further reduces the diameter In addition, starting member 12 may be removed from
thereof to form a glass optical fiber which possesses the the assembly before the second coating is applied or may
characteristics of the desired optical waveguide. That is, O be removed after both the first and second coatings are
it transmits preselected modes of light without excessive applied.
attenuation or absorption losses, minimizes cross-talk be Referring to FIG. 3, the removal of starting member
tween adjacent optical waveguides, does not cause exces 12 is illustrated. Starting member E2 is shown being
sive dispersion of the transmitted light, and provides an ground out by means of diamond reamer 24, however,
improved cladding-core interface. 5 any other means for accomplishing this result such, for
These and additional objects, features and advantages example, as hydrofluoric acid etching or core drilling are
of the present invention will become apparent to those also suitable.
skilled in the art from the following detailed description Since glass starting member 12 is ultimately removed,
and the attached drawing, on which, by way of example, the material of member 12 need only be such as to have
only the preferred embodiments of this invention are 20 a composition and coefficient of expansion compatible
illustrated. with the waveguide cladding and core materials. A suit
BRIEF ESCRIPTION OF THE DRAWINGS able material may be a normally produced glass iiaving
a composition similar to that of the cladding and core
FIG. is an illustration of a means of applying a materials although it does not need the high purity of
coating to the outside of a starting member. 25 such materials. It may be normally produced glass having
FIG. 2 is an illustration of a means of applying a sec ordinary or even an excessive level of impurity or en
ond coating to the outside peripheral surface of the first trapped bubbles that would otherwise render it unsuitable
coating. for effective light propagation. The starting member may
FIG. 3 is a fragmentary cross sectional elevation illus also be formed of graphite or the like.
trating a means of removing the starting member. 30 The materials of the core and cladding of an optical
FIG. 4 is a fragmentary elevation partly in cross-section waveguide should be produced from a glass having mini
of an optical fiber being formed. mum light absorption characteristics, and although any
FIG. 5 is a cross section taken along line 5-5 of optical quality glass may be used, a particularly suitable
FG, 4. glass from which to make an optical waveguide is fused
FIG. 5 is a cross section taken along line 6-6 of silica. For structural and other practical considerations,
FG, 4. it is desirable for the core and cladding glasses to have
DETALED DESCRIPTION OF THE INVENTION similar physical characteristics. Since the core glass must
have a higher index of refraction than the cladding for
It is to be noted that the drawings are illustrative and 40 proper operation, the core glass may desirably be formed
symbolic of the invention and there is no intention to indi of the same type of glass used for the cladding and doped
cate the scale or relative proportions of the elements with a small amount of some other material to slightly
shown therein. increase the index of refraction thereof. Therefore, if
One method of forming a clad optical fiber suitable for pure fused silica is used as the cladding glass, fused silica
use as an optical waveguide is illustrated in the drawings. doped with a material to increase the index of refraction
Referring to FIG. 1, a coating 10 of glass is applied to can be used as a core glass.
a substantially cylindrical glass starting member or rod There are many suitable materials that can satisfac
2 by means of a flame hydrolysis burner 4. Burner i4 torily be used as a dopant alone or in combination with
emits flame 6 in which a gas-vapor mixture is hydrolyzed each other. These include, but are not limited to, tita
to form a glass soot. The soot leaves flame 16 in a stream 50 nium oxide, tantalum oxide, tin oxide, niobium oxide,
18 and is directed toward starting member 12. The flame Zirconium oxide, aluminum oxide, lanthanum oxide, ger
hydrolysis method of forming coating 10 is hereinafter manium oxide, and boron oxide. The amount of dopant
described in detail. Starting member 12 is rotated for used should be kept to a minimum for various reasons.
uniform deposition of the soot. First, since additional doping material would cause the
Referring additionally to FIG. 2, a second coating 20 55 index of refraction to increase, the difference between the
of glass having a predetermined desired index of refrac index of refraction of the cladding glass and the core
tion is similarly applied over the outside peripheral sur glass will also increase requiring a decrease in the allow.
face of first coating 10 by the same flame hydrolysis able core diameter of the waveguide to obtain a wave
method heretofore noted. As illustrated in FIG. 2, the guide having the same operating characteristics, as here.
soot leaves flame 16 in a stream 22 and is directed to the 60 inafter explained. Second, if an excessive amount of dop
outside surface of coating 10. Similarly, coating 10 is ing material is added to the base material, a loss in light
rotated for uniform deposition of the second layer of transmission will result. Desirably, a small yet precise
soot. First coating 10 will form the core of the waveguide amount of dopant should be added to the base material
while second coating 20 will form the cladding. As will for the primary purpose of changing the index of refrac
be hereinafter described, the index of refraction of a 65 tion. For the purposes of the present invention, the
waveguide cladding must be less than the index of refrac amount of dopant is preferably maintained below about
tion of the core for proper operation. 15 percent, by weight of the total composition."
As will be understood, depending on the length of the VThe desired first and second coatings may be applied
coatings applied, a plurality of burners similar to burner by a variety of methods including but not limited to
44 may be positioned adjacent starting member 12 to 0. radio frequency Sputtering, sintering a coating of scot
provide a uniform distribution of soot along the longitu deposited by the flame hydrolysis process, chemical vapor
dinal axis of the starting member. Another way for deposition, depositing a glass frit, and the like. Clearly,
achieving uniform longitudinal distribution of soot is to the first and second coatings may be applied by either
translate starting member 12 along the longitudinal axis the same or different methods.
while the coatings are applied. 75 A particularly effective method of forming or apply.
... .-...--- - r
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3,737,292
6
ing a coating is accomplished by a flame hydrolysis proc where:
ess similar to that described in U.S. Patent No. 2,272,342
issued to J. F. Hyde or U.S. Patent No. 2,326,059 issued R=the cutoff value for the light mode or modes that
to M. E. Nordberg. A modification of the Nordberg proc are desired to be propagated through the fiber (R-
ess that will provide a titanium doped fused silica coating 2.405 when light mode HE11 is propagated)
is as follows. Dry oxygen is bubbled through a tank con a-radius of the core
taining a liquid mixture of approximately 53 percent by A=wavelength of transmitted light (sodium light
weight silicon-tetrachloride, SiCl, and 47 percent by 5893 A.)
weight titanium-tetrachloride TiCl4, which mixture is at n=core index of refraction
a temperature of approximately 35 C. SiCl, and TiCL 10. n2=cladding index of refraction
vapors picked up by the oxygen are then passed through An example of the means for determining the coor.
a gas-oxygen flame where they are hydrolyzed to form a dinated values of the core radius a, the core index of
soot, that is, minute glass particles, with a composition refraction n1, and the cladding index of refraction n.
of approximately 95 percent by weight SiO2 and 5 per may be as follows. When pure fused silica is chosen to
cent by weight TiO2. The glass soot leaves the flame in a 15 be the cladding glass, the index of refraction of the
steady stream, and is deposited on a rotating starting cladding would be aproximately 1.4584. An index of re
member. The thickness of the resulting coating is deter fraction of 1.4584 for fused silica is generally accepted for
mined by the amount of soot deposited which is pri sodium light having wavelength X=5893 A. Further, if the
marily controlled by the flow rates and the time allowed weight percentage of SiO2 and TiO, are selected so that
for deposition. The soot so applied is then sintered to 20 the core glass has a resulting index of refraction of 1466,
provide a dense, uniform coating. and the cutoff value is selected such that only the desired
A suitable cylindrical member is then formed by grind light mode or modes will propagate through the fiber, the
ing out or core drilling the starting member from the core diameter necessary to limit light propagation to such
composite structure. The outside and inside surfaces of desired mode or modes within the optical waveguide can
this cylinder are carefully polished and cleansed to re 25 then be determined by solving the above equation for
move surface irregularities and contamination which core radius a.
might later cause light scattering. Surface polishing may It has been found that light absorption properties may
be achieved by mechanical polishing, fire polishing, laser be further decreased and light transmission qualities fur.
milling, or the like. A particularly suitable method of ther improved in titanium oxide doped fused silica formed
smoothing the outside surfaces of the cylinder is accom 30 into optical waveguides, if the waveguides are drawn
plished by first mechanically polishing and thereafter in an oxygen atmosphere and then heat treated in a
flame polishing the mechanically polished surfaces. Hy suitable oxygen, nitrogen, or the like atmosphere. Such
drofluoric acid washing of the surfaces should be per heat treatment may consist of heating the waveguide in
formed before and after all polishing operations to avoid an oxygen atmosphere to between 500° C. and 1100° C.
contamination. 35 for not less than 0.5 minute. The length of heat treat
Coating 20 of glass is thereafter applied to the cylindri ment being related to the treatment temperature, that is,
cal glass member. The glass of the second coating must lower temperatures require longer heat treatment time
have suitable physical and optical properties, such as while heat treatment at higher temperatures requires a
viscosity, coefficient of expansion, and index of refraction. 40 shorter period of time.
A particularly effective means of forming coating 20 is After composite structure 26 is formed, it is either
to sinter a soot layer of the desired material applied by maintained at temperature or heated by furnace 28 as
the modified flame hydrolysis process heretofore de illustrated in FIG. 4. After the structure reaches a tem.
scribed. Since the index of refraction of the cladding and cosityperature at which the materials have a low enough vis
consequently the second coating glass must be lower than 45 for drawing, it is drawn until the cross sectional
that of the core, the glass of the second coating may be size thereof is reduced sufficiently to produce fiber 30.
of the same base material as the glass of the first coating Such a clad fiber thereafter forms the optical waveguide.
that will form the core except that it be undoped, or In FIG. 5 there is illustrated the cross sectional view of
doped to a lesser degree than that of the first coating. the composite structure 26 before it is drawn comprising
If coating 20 is applied by the modified flame hydrolysis 50 coatings 10 and 20. FIG. 6 illustrates the cross section
process heretofore described, the process parameters of fiber 30 drawn to the desired cross sectional dimen.
would be substantially the same, except that the starting sions. The total diameter to core diameter ratio for multi
liquid mixture would either not contain titanium-tetra mode optical waveguides is preferably in the range of
chloride so that the resulting coating would be SiO2 or 1001:1000 to 10:1, and for single mode waveguides in the
contain a lesser amount of titanium-tetrachloride so that range of 10:1 to 1000:1, although ratios outside of these
the resulting coating would be SiO2 doped to a lesser 55 ranges would also be operable.
degree than the core. A specific exafnple of a multimode waveguide produced
The necessary characteristics of an optical waveguide by the method of the present invention is as follows. A
to transmit a useable quantity of light is dependent upon starting member of fused quartz, approximately 4 inch
light energy not being lost through radiation due to light in diameter and about 10 inches long is sealed to a suitable
scattering centers, as well as not being excessively ab 60 handle. A liquid mixture containing 30.4 percent by
sorbed by the glass material. These centers are often weight TiCl4 and 69.6 percent by weight SiCl is heated
caused by tiny air bubbles or impurities in a waveguide to 35° C. Dry oxygen is bubbled through the liquid mix
at the core-cladding bond. The method of this invention ture and SiCl4 and TiCl, vapors are picked up by the .
combines an unusually clean and strong bond, thus elimi 65 oxygen. This vapor containing oxygen is then passed
nating most of such light scattering centers. Furthermore, through a gas-oxygen flame where the vapors hydrolyze
the present method minimizes the OH radical content. to form a steady stream of approximately 0.1 a.m.
To limit light propagation along an optical waveguide Sphere-like particles having a composition of 2.5 percent
to preselected modes, whether a single mode or multi by weight TiO, and 97.5% by weight SiO. The stream
mode operation is desired, the core diameter, the core is directed to the starting member and a soot layer of
index of refraction, and the cladding index of refraction 70 these particles is built up to about 1.5 inches in diameter.
must be coordinated according to the following equation. This layer of soot is then sintered in an induction furnace
having an oxygen atmosphere at about 1500° C. There.
2ard after, the outside of the sintered core glass is me
R= - W m n m? chanically polished to an RMS finish of approximately 5
75 microinches. The fused quartz starting member is then
 3,787,292
8
ground out by means of a diamond reamer. The tubular depositing a second layer of glass soot over the out
member so formed is rinsed in about a 50% hydrofluoric side peripheral surface of said first coating. by flame
acid solution, flame polished, and washed again in said hydrolysis, and
acid solution to provide a clean tubular member having heating said first coating and said second layer of glass
approximately 5% inch outer diameter. A second coating 5 soot until said second layer of soot sinters.
of 100 percent SiO is applied over the tubular member by 8. The method of claim 7 wherein sintering said sec
the same flame hydrolysis method described above except ond layer soot and drawing the structure is accomplished
that the liquid mixture does not contain TiCla. The SiO2 during the same heating step.
soot is applied until an outside diameter of approximately 9. The method of claim 7 wherein said second coating
1.5 inches is obtained. This structure is then placed in an 10 is fused silica and said first coating is fused silica doped
induction furnace wherein the SiO2 soot is sintered and with at least one material selected from the group con
the resulting composite structure drawn in an Oxygen sisting of titanium oxide, tantalum oxide, tin oxide, nio
atmosphere at about 2000 C. As the structure is drawn, bium oxide, zirconium oxide, aluminum oxide, lanthanum
it decreases in diameter and the central hole collapses. oxide, germanium oxide, and boron oxide.
Drawing is continued until the final desired waveguide lis 10. The method of claim 9 wherein said second coating
dimensions are obtained. Typical final waveguide dinnen is fused silica and said first coating is fused silica doped
sions may be a core diameter of 120 um. and a cladding with not more than 15 percent by weight of titanium
thickness of approximately 40 p.m. oxide. -
Although the present invention has been described with 11. The method of claim 9 wherein said heated struc
respect to specific details of certain embodiments thereof, 20 ture is drawn in a substantially oxygen atmosphere.
it is not intended that such details be limitations upon the 12. The method of claim 11 further comprising the
scope of the invention except insofar as set forth in the Step of heat treating said clad fiber in an oxygen atmos
following claims. phere.
We claim: 13. The method of claim wherein the first or second
1. A method of forming a clad optical fiber comprising 25 coating of glass is applied by radio frequency sputtering.
the steps of 14. The method of claim 1 wherein the first or second
providing a substantially cylindrical starting member, coating of glass is applied by chemical vapor deposition.
applying a first coating of glass to the outside periph 15. The method of claim 1 wherein the first or second
eral surface of said member, coating of glass is formed by applying a glass frit and
applying a second coating of glass having an index of 30 thereafter sintering said frit.
refraction less than that of the glass of said first 16. The method of claim 1 wherein said second coating
coating over the outside peripheral surface of said is fused silica and said first coating is fused silica doped
first coating, with not more than 15 percent by weight of titanium
removing said cylindrical starting member, oxide.
heating the structure so formed to the drawing tempera- 35 17. The method of claim 1 wherein said first and
ture of the materials thereof, and Second coatings of glass are formed by the steps com
drawing the heated structure to reduce the cross-sec prising
tional area thereof and to collapse said first coating depositing a first layer of glass soot on the outside pe.
of glass to form a clad fiber having a solid cross 40 ripheral surface of said member by flame hydrolysis,
section, said collapsed first coating forming the core depositing a second layer of soot over the outside pe
of: said fiber and said second coating forming the Epheral Surface of said first layer by flame hydrolysis,
fiber cladding. al
2. The method of claim 1 wherein said first coating heating the resulting assembly until each layer of glass
of glass is formed by the steps comprising soot sinters, said first sintered layer of soot forming
depositing a layer of glass soot on the outside periph said first coating and said second sintered layer of
eral surface of said member by flame hydrolysis, and soot forming said second coating.
heating said soot until it sinters.
3. The method of claim 2 wherein said starting mem References (Cited
ber is removed before said second coating is applied. 50 UNITED STATES PATENTS
4. The method of claim 3 wherein said starting mem
ber is removed by drilling further comprising the steps of 2,272,342 2/1942 Hyde -------------- 65-18 X
mechanically polishing the drilled surface, and 2,326,059 8/1943 Nordberg -------- 65-18 X
flame polishing the mechanically polished surface. 3,275,428 9/1966 Siegmund ... ------ 65-31 X
5. The method of claim 4 further comprising the steps 3,589,878 6/1971 Achener --------- 65-60 X
of 55 3,558,377 1/1971 Tantillo ----------. 65-4 X
mechanically polishing the exterior surface of said 3,659,915 5/1972. Maurer -------- 65-30 X
sintered first coating, and
flame polishing the mechanically polished surface. ROBERT L. LINDSAY, JR., Primary Examiner
6. The method of claim 5 further comprising the step U.S. C. X.R.
of hydrofluoric acid washing of said surfaces following 60
each polishing step. 65-4, 13, 18, 61, Dig. 7; 117-46 FS
7. The method of claim 2 wherein said second coating
of glass is formed by the steps comprising