(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property Organization

International Bureau l l l l l l l l l l l l l l l l l l l l l l l l l l l l l H l lMl l l l l
(43) International Publication Date (10) International Publication Number
PCT
27 December 2007 (27.12.2007) WO 2007/147946 A1
(51) International Patent Classification: AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, CA, CH,
C03B 37/018 (2006.01) C03B 37/014 (2006.01) CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG,
C23C 16/455 (2006.01) C03B 37/027 (2006.01) ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL,
C03B 37/012 (2006.01) IN, IS, JP, KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK,
LR, LS, LT, LU, LY, MA, MD, ME, MG, MK, MN, MW,
(21) International Application Number: MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PG, PH, PL,
PCT/FI2007/050373 PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY,
T J, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA,
(22) International Filing Date: 19 June 2007 (19.06.2007) ZM, ZW.

(25) Filing Language: Finnish

(84) Designated States (unless otherwise indicated, for every
kind of regional protection available): AR1PO (BW, GH,
(26) Publication Language: English
GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
(30) Priority Data:
European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
20065441 22 June 2006 (22.06.2006) FI
FR, GB, GR, HU, 1E, IS, IT, LT, LU, LV, MC, MT, NL, PL,
PT, RO, SE, SI, SK, TR), OAPI (BF, B J, CF, CG, CI, CM,
__ (71) Applicant (for all designated States except US): BENEQ
l GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG).
l
OY [FI/FI]; Ensimm iinen savu, FI-01510 Vantaa (FI).
l

-- (72) Inventors; and Declarations under Rule 4.17:

(75) Inventors/Applicants (for US only): SOININEN, Pekka -- as to applicant’s entitlement to apply for and be granted a
l patent (Rule 4.17(ii))
l [FUFI]; Ilmarinkatu 10 B 28, FI-00100 Helsinki (FI).
-- of inventorship (Rule 4.17(iv))
l SNECK, Sami [FI/FI]; Keih istie 28 F, FI-01280 Vantaa
l
l (FI).
l Published:
(74) Agent: KOLSTER OY AB; Iso Roobertinkatu 23, PO -- with international search report
l
l
l Box 148, FI-00121 Helsinki (FI).
l
For two-letter codes and other abbreviations, refer to the "Guid-
(81) Designated States (unless otherwise indicated, for every ance Notes on Codes and Abbreviations" appearing at the begin-
l
kind of national protection available): AE, AG, AL, AM, ning of each regular issue of the PCT Gazette.
l

l
l

m
m
m
m
m
m
m
m

m
m
m
m
m
m

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(54) Title: METHOD FOR MANUFACTURING FIBRE PREFORM

I"-
(57) Abstract: The invention relates to a method for manufacturing a fibre preform and/or for modifying properties of the same
by an ALD method. According to the invention, one or more fibre preforms are placed in an atomic layer deposition reactor and a
first catalyst is supplied into a core of the fibre preform in order to produce a catalysing layer onto a surface of the core of the fibre
reform. Next, one or more dopants are supplied into the core of the fibre preform, whereby the first catalyst causes two or more
deposition layers to be formed onto the surface of the core of the fibre preform.
 WO 2007/147946 PCT/FI2007/050373

1
METHOD FOR MANUFACTURING FIBRE PREFORM

BACKGROUND OF THE INVENTION

[0001] The invention relates to manufacturing or modifying a fibre
preform by an atomic layer deposition method, and particularly the present in-
5 vention relates to a method according to the preamble of claim 1 for manufac-
turing a fibre preform and/or for modifying properties of the same by an ALD
method, wherein a surface to be grown is exposed to alternately repeated
saturated surface reactions of starting materials in accordance with principles
of the ALD method. The present invention further relates to a fibre preform
10 manufactured or modified by the method according to the invention as well as
to an optical fibre manufactured from a fibre preform manufactured or modified
according to the present invention.
[0002] According to prior art, the manufacture of a core of a fibre
preform is carried out e.g. by a Modified Chemical Vapour Deposition or MCVD
15 method. In the MCVD method, the aim is to grow, by using a Chemical Vapour
Deposition or CVD technique, a so-called soot layer inside a tubular preform in
a longitudinal direction thereof. In order to produce fibres of uniform quality
during manufacture, process parameters have to be adjusted extremely accu-
rately, but despite such accuracy, growth takes place in a different manner at
20 an inlet end and at an outlet end of the preform. Furthermore, as the process
of growing the core of the fibre preform progresses, the conditions change as
the diameter of the core of the preform decreases due to the grown soot layer.
In practice, this means that the properties also in the direction of a radius of the
preform change. The manufacture of the core of the preform takes place layer
25 by layer to enable a refractive index distribution to be formed to be adjusted.
This, in turn, leads to the requirement that the starting materials, together with
a substrate, should be distributed uniformly on the surface of the core of the
preform which, consequently, means that the process becomes more demand.-
ing to manage. The soot layer provided is made of a porous material, so it has
30 to be sintered to make it solid prior to the manufacture of a next layer. Thus,
the requirements not only of the process but also of the sintering have to be
taken into account in the adjustment of a flame used in the sintering. The core
of the fibre preform may also be manufactured by utilizing some other method
used in the manufacture of a fibre preform, such as OVD, VAD or another
35 corresponding method.
 WO 2007/147946 PCT/FI2007/050373

2
[0003] This manufacture of a core of a fibre preform by the MCVD
method or some other method for manufacturing fibre is an extremely accurate
and demanding task and the required equipment is complex, as can be seen in
what has been disclosed above. Despite such accuracy, it is impossible to
manufacture a core of a fibre preform with an ideal accuracy and at a desired
production rate, but the process is slow and the end product always includes
compromises. Furthermore, between the core growing and sintering phases,
the soot layer tends to absorb impurities, which impair the properties of a fin-
ished end product.
10 [0004] It has not been economically possible nor reasonable to
manufacture a fibre preform or its core by means of a conventional ALD tech-
nique since the conventional technique has allowed only one atomic layer to
be grown at a time onto the surface of the core of the fibre preform. As far as
the purposes of commercial production are concerned, by this known method it
15 has been far too slow to achieve a sufficient thickness of the deposition layers.

BRIEF DESCRIPTION OF THE INVENTION

[0005] An object of the invention is thus to provide a method so as
to solve the above-mentioned problems. The object of the invention is
achieved by a method according to the characterizing part of claim 1, which is
20 characterized by the method comprising the following steps of:
a) supplying a catalyst to an ALD reactor in order to produce a cata-
lysing surface onto the surface of the fibre preform to be grown;
b) supplying one or more dopants and/or substrates onto the sur-
face of the fibre preform to be grown so that the catalyst causes two or more
25 atomic or molecular layers to be formed onto the surface of the fibre preform to
be grown.
[0006] Preferred embodiments of the invention are disclosed in the
dependent claims.
[0007] The idea underlying the invention is that a digitally accurate
30 Atomic Layer Deposition or ALD method is used for manufacturing and/or
modifying a fibre preform, particularly for manufacturing and/or modifying a
core of a fibre preform. The ALD method and its applications relating to doping
of a fibre preform and other materials have been further described e.g. in Fin-
nish Patent Application No. 20045490 of the same Applicant. According to the
35 invention, a substrate and/or a dopant of a fibre preform is supplied by the ALD
 WO 2007/147946 PCT/FI2007/050373

method to a surface of the fibre preform to be grown. According to the inven-

tion, the ALD method for manufacturing a fibre preform utilizes a so-called
catalytic ALD deposition such that the surface of the fibre preform to be grown,
the fibre preform having been placed inside an ALD reactor, is first exposed to
5 a catalyst which reacts with the surface of the fibre preform, forming a catalytic
surface. Next, the surface of the fibre preform to be grown is exposed to a
substrate and/or a dopant in order to produce deposition layers onto the sur-
face of the fibre preform to be grown and/or in order to dope the substrate of
the fibre preform with the dopant. Because of the catalyst, the number of
10 atomic or molecular layers being formed onto the surface of the fibre preform
to be grown is not only one but the catalyst enables the surface reaction of the
substrate and/or the dopant to continue such that during one cycle, which
comprises exposing the surface to be grown once to the catalyst and once to
the substrate and/or dopant, two or more atomic or molecular layers are
15 formed onto the surface of the fibre preform to be grown, together forming a
deposit layer produced by one cycle. Catalysed reactions are temperature and
dose dependent such that it is possible to adjust the number of atomic and mo-
lecular layers and thus the thickness of the deposition layer being formed by
means of process temperatures as well as the magnitude of doses of catalyst
20 and/or substrate and/or dopant supplied onto the surface of the fibre preform to
be grown.
[0008] The reactions of the substrate and/or the dopant catalysed
by a catalyst enable even large deposition layers to be formed onto the surface
of the fibre preform to be grown during each ALD cycle. A large deposition
25 layer herein refers to the formation of two or more atomic or molecular layers
during one ALD cycle, preferably to the formation of ten or more atomic or mo-
lecular layers during one cycle, or even to the formation of 30 to 100 atomic or
molecular layers during one ALD cycle. According to the invention, such a
catalytic ALD deposition enables an extremely rapid ALD deposition, whereby
30 it becomes possible to manufacture or modify a fibre preform by the ALD
method for commercial production. In addition, while the use of ALD becomes
possible, it becomes possible to manufacture fibre preforms of higher quality
since as a method, ALD provides a digitally accurate fibre preform manufac-
ture which allows the amounts and ratios of the dopants to be adjusted accu-
35 rately. Furthermore, the equipment used in the ALD method can be designed
to be significantly simpler than the complex equipment of the MCVD method.
 WO 2007/147946 PCT/FI2007/050373

4
No sintering phase, which is required in an MCVD process, is thus needed,
either, Hence, in terms of quality, pureness and accuracy, a fibre preform
manufactured by the method as well as an optical fibre further manufactured
therefrom are better than those manufactured by the known methods.

5 DETAILED DESCRIPTION OF THE INVENTION

[0009] In the following, the manufacture of a core of a tubular fibre
preform by a method according to the invention is examined by way of exam-
ple. According to the present invention, ALD technique is utilized for the manu-
facture of a fibre preform and/or a core thereof. In the present context, a fibre
10 preform refers to any fibre preform which is suitable for manufacturing an opti-
cal fibre. Furthermore, in the present context, the manufacture of a fibre pre-
form may comprise the manufacture of a fibre preform itself, the manufacture
of a core of a fibre preform, modifying a fibre preform and/or modifying a core
of a fibre preform. In other words, the method according to the invention may
15 be utilized in a part of a manufacturing process of a fibre preform or its core, or
in the entire process.
[0010] For the method according to the invention, an ALD appara-
tus, an ALD reactor in particular, in which one or more fibre preforms are
placed, is provided. The ALD reactor is preferably provided with a reaction
2O chamber in which preforms are placed such that the starting materials may be
supplied into the tubular preform, i.e. to a core of the preform. In practice, this
can be implemented by placing the preforms between inlets and outlets of the
reaction chamber such that from the inlet the starting materials flow into the
core of the preform from its first end and exit the preform from its second end,
25 directly to the outlet. Thus, only the core of the preform is exposed to the start-
ing materials. When two or more preforms are to be placed in the ALD reactor,
it is possible to provide the reaction chamber with an inlet and outlet for a lar-
ger number of preforms. This enables fibre preforms having different properties
to be manufactured simultaneously in the ALD reactor by feeding different
30 starting materials and/or amounts or ratios of starting materials to different pre-
forms.
[0011] Preferably, however, the ALD reactor may be provided such
that the preforms may be placed in the reaction chamber successively in a flow
connection with one another. In such a case, a starting material fed into a first
35 preform passes through all preforms before exiting the reactor. In other words,
 WO 2007/147946 PCT/FI2007/050373

5
the preforms may be attached by appropriate attaching means provided in the
reactor which allow the starting materials supplied into the core of the preforms
to flow successively through all the preforms. This enables preforms to be
manufactured efficiently since it is possible to process several preforms simul-
5 taneously during the same starting material cycle. In addition to connecting the
preforms in series as disclosed above, preforms may also be placed in the
ALD reactor in parallel, in which case a catalyst and/or a substrate and/or a
dopant is fed to each preform separately, simultaneously or non-
simultaneously. The preforms are placed normally in the reaction chamber,
10 which may be e.g. a vacuum chamber, of the ALD reactor. Alternatively, the
preforms may be provided in the ALD reactor such that the tubular preforms
themselves constitute the walls of the reaction chamber to which the starting
materials, such as the catalyst, substrate and dopant, are fed, in which case no
separate vacuum chamber is necessarily needed but in some cases the pre-
15 forms may form this vacuum chamber. Furthermore, the method according to
the invention may be carried out by the ALD technique also in a device for the
manufacture of a preform or in a device for the modification thereof, such as an
MCDV lathe, or during the manufacture of a preform.
[0012] Preforms are made of a glass material, which may be any
20 oxide forming conventional glass, such as SiO2 , B2 03 , GeO2 and P4 010 .
[0013] As described above, according to the invention a catalyst,
which forms a catalysing layer onto the surface of the core as a result of a sur-
face reaction of the surface of the core and the catalyst, is first supplied into
the core of the tubular preforms provided in the ALD reactor. A catalyst to be
25 used may be trimethylaluminium (Me3 AI), which reacts with OH groups resid-
ing on the surface of the core of the preform, forming aluminium-oxygen bonds
and a surface comprising methylaluminium. Alternatively, aluminium dimethyl-
amide (AI2 (NMe2 )6 ) may be used as a catalyst. In addition to the above-
mentioned aluminium compounds, trimethyl lanthanum, trimethyl zirconium,
30 trimethyl hafnium or a compound of another trimethyl and metal or another
compound comprising aluminium, lanthanum, zirconium, hafnium or another
metal, which causes a catalysing effect in order to grow a plurality of atomic
layers onto the surface of the core of the fibre preform during one cycle, can be
used as a catalyst. In such a case, the catalyst each time forms onto the sur-
35 face of the core a metal-oxygen bond and/or a surface comprising methyl
 WO 2007/147946 PCT/FI2007/050373

metal and having a catalytic effect, thus forming a catalytic layer onto the sur-
face of the core of the preform.
[0014] Next, one or more dopants and/or substrates are supplied
into the core of the preform, whereby a first catalyst causes the formation of
two or more atomic or molecular layers onto the surface of the core of the fibre
preform. In other words, the catalyst enables two or more atomic layers to be
formed onto the surface of the core by catalysing a surface reaction of the sub-
strate and/or the dopant. In the present connection, silanol, such as tris(tert-
butoxy)silanol ((ButO)3 SiOH), which reacts with the catalytic surface, can be
10 used as a substrate. When the aforementioned silanol is used together with
aluminium dimethylamide, a siloxane polymer is formed which forms bonds
through an aluminium layer. When said silanol is further supplied into the core
of the preform, it diffuses through the previously formed deposition layers to
the aluminium-oxygen bonds, forming a new deposition layer beneath the
15 previous ones by means of the above-described mechanism. This catalysed
reaction progresses until said silanol is no longer capable of diffusing to the
aluminium-oxygen bonds through the previous deposition layers. This reaction
mechanism and catalytic effect have been disclosed and explained in more
detail e.g. in publication "Rapid Vapor Deposition of Highly Conformal Silica
20 Nanolaminates", Science, VOL 298, 11 OCTOBER 2002, pp. 402 to 406.
Another silanol or another corresponding substance or compound which en-
ables a catalytic ALD process may also be used as a substrate.
[0015] The core of the preform may also be provided with a dopant,
which may be added to the substrate or it may be supplied thereto separately,
25 simultaneously or non-simultaneously with the substrate. Any material used for
a normal doping of the fibre preform may be used as a dopant. These dopants
may thus comprise one or more materials or compounds, and the dopant may
be in elementary or compound form. For instance, the dopant may comprise a
rare earth metal, such as erbium, ytterbium, neodymium or cerium, a material
30 of boron group, such as boron or aluminium, a material of carbon group, such
as germanium, tin and silicon, a material of nitrogen group, such as phospho-
rus, a material of fluorine group, such as fluorine, or silver or any material or
compound suitable for doping. In the method according to the invention, the
dopant may be an additive, auxiliary substance, filling material, colouring agent
35 or another additional material of the material to be doped. Particularly, the
dopant may be an auxiliary, reinforcement, softener, pigment or a sintering
 WO 2007/147946 PCT/FI2007/050373

7
additive for thermal, light or electrical conductivity. The dopant may be supplied
into the core of the fibre preform also by carrying out an ordinary ALD cycle
without the assistance of a catalyst. In such a case, in order to grow the core of
the fibre preform, a catalyst and a substrate may be supplied into the core of
5 the fibre preform by utilizing catalytic ALD cycles while the dopant, in turn, is
supplied in separate ALD cycles to be carried out between the catalytic cycles.
[0016] In accordance with what has been disclosed above, during
one ALD cycle, wherein first, a dose of catalyst and next, a dose of a substrate
and/or dopant are supplied into the core of the preform, due to the influence of
10 the catalyst it is possible to form a deposition layer having a thickness of sev-
eral atomic layers. This makes a core of a fibre preform fast to manufacture as
well as preforms and thus an optical fibre of extremely high quality to be pro-
duced since it is possible to utilize the digitally accurate ALD method while
growth of the material takes place three-dimensionally.
15 [0017] In the method, the reaction of the catalyst and substrate
and/or dopant supplied into the core of the preform may be adjusted by heat-
ing the preform after it has been placed in the ALD reactor by heating means
to a first predetermined temperature and/or by heating the preform to a second
predetermined temperature after feeding the catalyst prior to feeding the sub-
20 strate and/or the dopant. Thus, the temperature of the fibre preform is adjusted
in order to produce a predetermined number of deposition layers onto the sur-
face of the core of the fibre preform and/or in order to produce a predetermined
thickness of deposition layers onto the surface of the core of the fibre preform.
This is possible since the reactions of the catalyst and e.g. silanol are tempera-
25 ture-dependent. Thus when silanol and trimethylaluminium are used, the tem-
perature is preferably 200 to 300 °C. This temperature is low compared to the
temperatures of known methods for manufacturing and modifying a preform.
Hence, in the method according to the invention, the glass material does not
soften, which enables the above-disclosed use of a tubular preform as a reac-
30 tion chamber.
[0018] When necessary, an ALD cycle, which comprises supplying
a catalyst as well as a substrate and/or a dopant, can be repeated as many
times as desired in order to produce a desired or predetermined deposition
layer or a desired doping structure into the core of the fibre preform. The same
35 catalyst, dopant and substrate may be used in successive cycles or, alterna-
tively, the catalyst and/or dopant and/or substrate may be changed between
 WO 2007/147946 PCT/FI2007/050373

8
cycles so as to provide the fibre preform with the desired properties. In addi-
tion, the mutual ratio or amount of catalyst, substrate and/or dopant may be
varied between different cycles. Furthermore, in each cycle it is also possible
to supply one or more dopants into the core of the fibre preform simultane-
5 ously; similarly, two or more substrates and/or catalysts may also be used in
one cycle.
[0019] It is to be noted that although the manufacture and/or modifi-
cation of a core of a tubular preform by utilizing the method according to the
present invention has been disclosed above by way of example, this method
10 may also be used for manufacturing or modifying a cladding of a preform by
exposing this cladding to the catalytic ALD method. It is further to be noted that
the core of the fibre preform may be grown or formed also from inside out in-
stead of from outside in, as disclosed above. In such a case, the core of the
preform is grown around e.g. a wire or a rod.
15 [0020] In accordance with the above, the accurate and highly man-
ageable manufacturing method enables a fibre preform whose properties are
of higher quality than those of a prior art fibre preform to be manufactured. Fur-
thermore, the fibre preform may be manufactured quickly and economically,
and further, its properties may be adjusted extremely accurately during manu-
20 facture. From a fibre preform thus provided, an optical fibre may be further
manufactured which is of higher quality than that of the prior art, whereby, as a
result of the more accurate method of manufacturing the fibre preform, it has a
more accurate structure.
[0021] The catalytic ALD method according to the present invention
25 may also be utilized in other applications. Such applications include hermetic
coating, i.e. encapsulating, antireflective coating, active optical filters enabling
e.g. band-pass filters to be provided, coating or encapsulating of fuel cells and
solar panels, coating or passivating of pieces of jewellery, as well as coating,
encapsulating or passivating of other metals, as well as Micro-Electro-
30 Mechanical Systems or MEMS applications. In all these applications, the
above-described catalytic ALD method is utilized such that the product being
processed is placed in an ALD reactor wherein it is processed according to
what has been disclosed above in order to achieve the desired properties. In
other words, these other applications are carried out by replacing a fibre pre-
35 form disclosed above by a product to be processed or a product whose proper-
ties are to be modified. Until now, this has not been possible by the ALD
 WO 2007/147946 PCT/FI2007/050373

9
method due to its slowness, but now this catalytic method enables fast produc-
tion of deposit layers with the growth rate being up to 100 times or more com-
pared with the conventional ALD method.
[0022] It is apparent to one skilled in the art that as technology ad-
5 vances, the basic idea of the invention may be implemented in many different
ways. The invention and its embodiments are thus not restricted to the above-
described examples but may vary within the scope of the claims.
 WO 2007/147946 PCT/FI2007/050373

10

CLAIMS
1. A method for manufacturing a fibre preform and/or for modifying
properties of the same by an ALD method, wherein a surface to be grown is
exposed to alternately repeated saturated surface reactions of starting mated-
5 als in accordance with principles of the ALD method, c h a r a c t e r i z e d by
the method comprising the following steps of:
a) supplying a catalyst to an ALD reactor in order to produce a cata-
lysing surface onto the surface of the fibre preform to be grown;
b) supplying one or more dopants and/or substrates onto the sur-
10 face of the fibre preform to be grown so that the catalyst causes two or more
atomic or molecular layers to be formed onto the surface of the fibre preform to
be grown.
2. A method as claimed in claim 1, c h a r a c t e r i z e d by repeat-
ing steps a) and b), which constitute one cycle, again once or more times when
15 necessary.
3. A method as claimed in claim 1 or 2, characterized by
supplying in step c) one dopant and/or substrate into a core of the fibre pre-
form.
4. A method as claimed in claim 3, c h a r a c t e r i z e d by supply-
20 ing, when steps b) and c) are repeated, in a next cycle a catalyst and/or dopant
and/or substrate different than that in the previous cycle onto the surface of the
fibre preform to be grown.
5. A method as claimed in claim 3, c h a r a c t e r i z e d by supply-
ing, when steps b) and c) are repeated, in a next cycle a same catalyst as
25 and/or a different dopant and/or substrate than that in the previous cycle onto
the surface of the fibre preform to be grown.
6. A method as claimed in any one of the preceding claims 1 to 5,
c h a r a c t e r i z e d by using trimethylaluminium as a catalyst.
7. A method as claimed in any one of the preceding claims 1 to 5,
30 c h a r a c t e r i z e d by using as a catalyst trimethyl lanthanum, trimethyl zir-
conium, trimethyl hafnium or a compound of another trimethyl and metal or a
compound comprising another aluminium, lanthanum, zirconium, hafnium or a
another metal, which causes a catalysing effect in order to grow a plurality of
atomic or molecular layers onto the surface of the core of the fibre preform dur-
35 ing one cycle.
 WO 2007/147946 PCT/FI2007/050373

11
8. A method as claimed in claim 7, characterized by the
dopant comprising erbium, ytterbium, neodymium, cerium, boron or aluminium,
germanium, tin, phosphorus, fluorine, or silver or any other material suitable for
doping a fibre preform.
5 9. A method as claimed in any one of the preceding claims 1 to 8,
c h a r a c t e r i z e d by the substrate comprising silanol, glass or oxide form-
ing a glass material.
10. A method as claimed in any one of the preceding claims 1 to 9,
c h a r a c t e r i z e d by heating the fibre preform to a first predetermined tem-
10 perature prior to step a), and/or to a second predetermined temperature after
step a) prior to step b).
11. Amethod as claimed in claim 10, characterized by ad-
justing the temperature of the fibre preform in order to produce a predeter-
mined number of atomic or molecular layers onto the surface of the fibre pre-
15 form to be grown and/or in order to produce a predetermined thickness of a
deposition layer onto the surface of the fibre preform to be grown.
12. A method as claimed in any one of the preceding claims 1 to 11,
ch a ra cte rize d by adjusting the amount of catalyst and/or substrate
and/or dopant to be supplied to the ALD reactor in one cycle in order to pro-
20 duce a predetermined number of atomic or molecular layers onto the surface
of the fibre preform to be grown and/or in order to produce a predetermined
thickness of a deposit layer onto the surface of the fibre preform to be grown.
13. A method as claimed in any one of the preceding claims 1 to 12,
c h a r a c t e r i z e d by providing two or more fibre preforms that are arranged
25 successively in a flow connection with one another such that a catalyst and a
dopant and/or a substrate supplied into a core of a first tubular fibre preform
flows through the core of all fibre preforms.
14. A method as claimed in any one of the preceding claims 1 to 12,
c h a r a c t e r i z e d by providing two or more tubular fibre preforms that are
3O arranged parallelly so as to enable a catalyst and a dopant and/or a substrate
to be supplied to the core of each of them simultaneously or non-
simultaneously.
15. A method as claimed in any one of the preceding claims 1 to 14,
c h a r a c t e r i z e d by carrying out the method such that the tubular preforms
35 themselves constitute walls of a reaction chamber.
 WO 2007/147946 PCT/FI2007/050373

12
16. A method as claimed in any one of the preceding claims 1 to 14,
c h a r a c t e r i z e d by exposing the surface of the preform to be grown to a
dopant by utilizing an ordinary ALD technique without using a catalyst.
17. A method as claimed in any one of the preceding claims 1 to 16,
5 c h a r a c t e r i z e d by carrying out the method in a device for manufacturing
and/or modifying a preform.
18. A fibre preform for the manufacture of an optical fibre, c h a r-
a c t e r i z e d in that the fibre preform has been manufactured or modified by
a method according to claims 1 to 17.
10 19. An optical fibre manufactured from a fibre preform, c h a r a c-
t e r i z e d in that the fibre preform has been manufactured or modified by a
method according to claims 1 to 17.
 INTERNATIONAL SEARCH REPORT International application No.

PCT/FI2007/050373

A. CLASSIFICATION OF SUBJECT MATTER

See extra sheet

According to International Patent Classification (]PC) or to both national classification and ]PC
B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)

IPC 8: C03B, C23C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

FI, SE, DK, NO

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal, WPI, NPL

c. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

Y FI 20055166 A (BENEQ OY) 03 February 2006 (03.02.2006), claim 1; 1-19

page 4, line 35 # page 5, line 10; page 10, lines 19-28; claim 13

Y WO 03083167 A1 (HARVARD COLLEGE et al.) 09 October 2003 1-19

(09.10.2003), abstract, pages 2 and 3; page 10, lines 1-11; page 30, line14
# page 31, line 5; page 23, lines 3-8

[] Further documents are listed in the continuation of Box C. [] See patent family annex.

* Special categories of cited documents: "T" later document published after the international filing date or priority
document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand
"A"
to be of particular relevance the principle or theory underlying the invention

"E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot be
filing date considered novel or cannot be considered to involve an inventive
"L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone
cited to establish the publication date of another citation or other ,,y,, document of particular relevance; the claimed invention cannot be
special reason (as specified) considered to involve an inventive step when the document is
"O" document referring to an oral disclosure, use, exhibition or other means combined with one or more other such documents, such combination
"p" document published prior to the international filing date but later than being obvious to a person skilled in the art
the priority date claimed ,, &,, document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

26 September 2007 (26.09.2007) 12 October 2007 (12.10.2007)

Name and mailing address of the ISA/FI Authorized officer
National Board of Patents and Registration of Finland Matti Pasanen
P.O. Box 1160, FI-00101 HELSINKI, Finland
Facsimile No. +358 9 6939 5328 Telephone No. +358 9 6939 500

Fo Tn PCT/ISA/210 (second sheet) (April 2007)

 INTERNATIONAL SEARCH REPORT International application No.
Information on patent family members
PCT/FI2007/050373

Patent document Publication Patent family Publication

cited in search report date members(s) date

FI 20055166 A 03/02/2006 EP 1776321 A1 25/04/2007

CA 2568002 A1 05/01/2006
WO 2006000643 A1 05/01/2006

WO 03083167 A1 09/10/2003 US 2005112282 A1 26/05 005

JP 2005521792T T 21/07 005
EP 1490529 A1 29/12 004
CN 1650044 A 03/08 005
AU 2003228402 A1 13/10 003

FmTn PCT/ISA/210 (patent family annex) (April 2007)

 INTERNATIONAL SEARCH REPORT
International application No.
PCT/FI2007/050373

CLASSIFICATION OF SUBJECT MATTER

Int.CI.
003B 37/018 (2006.01)
0230 16/455 (2006.01)
C03B 37/012 (2006.01 )
C03B 37/014 (2006.01 )
C03B 37/027 (2006.01 )

Form PCT/ISA/210 (Extra sheet) (April 2007)