U.S. patent application number 11/328246 was filed with the patent office on 2006-11-16 for optical fiber with quantum dots.
Invention is credited to Erik Herz, Carvel Holton, Kenith Meissner, Corey Paye.
Application Number | 20060257088 11/328246 |
Document ID | / |
Family ID | 34595866 |
Filed Date | 2006-11-16 |
United States Patent
Application |
20060257088 |
Kind Code |
A1 |
Herz; Erik ; et al. |
November 16, 2006 |
OPTICAL FIBER WITH QUANTUM DOTS
Abstract
Holey optical fibers (e.g. photonic fibers, random-hole fibers)
are fabricated with quantum dots disposed in the holes. The quantum
dots can provide light amplification and sensing functions, for
example. When used for sensing, the dots will experience altered
optical properties (e.g. altered fluorescence or absorption
wavelength) in response to certain chemicals, biological elements,
radiation, high energy particles, electrical or magnetic fields, or
thermal/mechanical deformations. Since the dots are disposed in the
holes, the dots interact with the evanescent field of core-confined
light. Quantum dots can be damaged by high heat, and so typically
cannot be embedded within conventional silica optical fibers. In
the present invention, dots can be carried into the holes by a
solvent at room temperature. The present invention also includes
solid glass fibers made of low melting point materials (e.g.
phosphate glass, lead oxide glass) with embedded quantum dots.
Inventors: |
Herz; Erik; (Ithaca, NY)
; Holton; Carvel; (Blacksburg, VA) ; Meissner;
Kenith; (College Station, TX) ; Paye; Corey;
(Blacksburg, VA) |
Correspondence
Address: |
WHITHAM, CURTIS & CHRISTOFFERSON & COOK, P.C.
11491 SUNSET HILLS ROAD
SUITE 340
RESTON
VA
20190
US
|
Family ID: |
34595866 |
Appl. No.: |
11/328246 |
Filed: |
January 10, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10863823 |
Jun 9, 2004 |
7054513 |
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11328246 |
Jan 10, 2006 |
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60476650 |
Jun 9, 2003 |
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60543620 |
Feb 12, 2004 |
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Current U.S.
Class: |
385/125 |
Current CPC
Class: |
G02B 6/02347 20130101;
G02B 6/02371 20130101; H01S 3/06741 20130101; B82Y 20/00 20130101;
C03C 4/0071 20130101; H01S 3/06708 20130101; H01S 3/169 20130101;
G02B 6/02385 20130101; G02B 6/032 20130101; C03C 14/006 20130101;
C03C 3/102 20130101; G02B 6/02357 20130101; C03C 14/004 20130101;
C03C 3/321 20130101; C03C 3/097 20130101; G02B 6/02366 20130101;
C03C 4/12 20130101; G02B 6/1225 20130101; C03C 13/046 20130101;
G02B 2006/0325 20130101; G02B 6/0229 20130101 |
Class at
Publication: |
385/125 |
International
Class: |
G02B 6/032 20060101
G02B006/032 |
Claims
1. A holey optical fiber comprising: a) a guiding region for
carrying confined light; b) a plurality of holes in the optical
fiber, wherein light confined to the guiding region exists as an
evanescent wave in the holes; c) a plurality of quantum dots in the
holes.
2. The holey optical fiber of claim 1 wherein the holey optical
fiber is a photonic crystal-holey fiber or an index-guiding holey
fiber.
3. The holey optical fiber of claim 1 wherein the holey optical
fiber is a random-hole optical fiber.
4. The holey optical fiber of claim 1 wherein the holes are
disposed in a cladding region of the optical fiber.
5. The holey optical fiber of claim 4 further comprising a solid
core surrounded by the cladding region.
6. The holey optical fiber of claim 1 wherein the holes are
disposed in a core region of the optical fiber.
7. The holey optical fiber of claim 1 further comprising a solvent
disposed in the holes.
8. The holey optical fiber of claim 1 wherein the quantum dots are
suspended in a solvent, colloid, gelatin or solid host.
9. The holey optical fiber of claim 1 wherein the quantum dots are
supported by sidewalls of the holes.
10. The holey optical fiber of claim 1 further comprising a
conventional solid fiber fusion spliced to the holey optical fiber
so that the quantum dots are sealed within the holey optical
fiber.
11. The holey optical fiber of claim 1 wherein the holes have a
refractive index lower than the optical fiber material.
12. The holey optical fiber of claim 1 wherein the holes are sealed
on at least one end so that the quantum dots are encapsulated
within the fiber.
13. An optical fiber made of a glass having a drawing temperature
less than 700 Celsius, and comprising quantum dots embedded within
the glass.
14. The optical fiber of claim 13 wherein the quantum dots are
embedded in the glass by an extrinsic doping processes.
15. The optical fiber of claim 13 wherein the fiber is made of a
material selected from the group consisting of phosphate glass,
lead glass and chalcogenide polymers.
16. The optical fiber of claim 13 wherein the glass comprises at
least 35% by weight lead oxide.
17. The optical fiber of claim 13 wherein the drawing temperature
is less than a boiling temperature of the quantum dot material.
18. The optical fiber of claim 13 wherein the glass has a drawing
temperature less than 500 Celsius.
19. The optical fiber of claim 13 wherein the quantum dots are made
of a material selected from the group consisting of tellurides and
antimonides.
20. The optical fiber of claim 13 wherein the fiber comprises a
core and a cladding, and wherein the quantum dots are disposed in
the core.
21. The optical fiber of claim 13 wherein the fiber comprises a
core and a cladding, and wherein the quantum dots are disposed in
the cladding.
22-28. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of priority from
co-pending provisional applications 60/476,650 filed on Jun. 9,
2003 and 60/543,620, filed on Feb. 12, 2004, the complete contents
of which are herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention provides optical fibers (holey fibers
or low melting point glass fibers) containing quantum dots. The
present invention relates generally to fiber-based sensors, lasers,
modulators, wavelength converters, filters, linear and non-linear
elements.
BACKGROUND OF THE INVENTION
[0003] Quantum dots are nanometer-scale particles (e.g., typically
1-10 nanometers in diameter) of metal, dielectric or semiconductor
material. Quantum dots are commonly made of compound semiconductors
such as CdSe, ZnSe, or PbS and may be manufactured in solid hosts,
films, suspensions or other material formats Quantum dots are well
known for providing useful optical properties when incorporated
into polymeric and glass materials. Specifically, quantum dots can
provide optical amplification, saturable absorption, or nonlinear
effects for example. As understood in the art, the term quantum dot
may apply to particles in the form of spheres, rods, wires, etc.
The term `quantum dot` herein refers to any such forms as are known
in the art.
[0004] U.S. Pat. No. 5,881,200 to Burt, for example teaches an
optical fiber with a hollow core filled with a quantum dot colloid.
The quantum dots provide an optical gain medium that can be used as
a laser amplifier. Similarly, U.S. Pat. No. 5,260,957 to Hakimi et
al. teaches a polymeric optical waveguide containing quantum dots
that provide lasing capability. U.S. Pat. No. 6,710,366 also
teaches matrix composite materials with quantum dots having
nonlinear optical properties.
[0005] Incorporating quantum dots into optical fibers and
waveguides can be problematic because of the sensitive nature of
quantum dots. For example, many quantum dots are not able to
withstand high temperatures (e.g., above 1000C) required for
melting glass or silica. Specifically, quantum dots from compound
semiconductors can dissociate or diffuse into glass at high
temperatures. Quantum dots typically cannot be directly
incorporated into a silica optical fiber because they will be
destroyed during the high heat (e.g. 1500C) drawing process. Also,
quantum dots can be damaged by oxidation.
[0006] Many quantum dots provide superior electronic and optical
properties when they are coated with a core shell material such as
TOPO. Such core shells can prevent oxidation and enhance electron
confinement, and may even be essential in some applications.
However, core shell materials are often polymeric and are often
destroyed by high temperatures.
[0007] However, there are many potential applications for optical
fibers (particularly glass fibers) having quantum dots. It would be
an advance in the art to provide glass optical fibers having
quantum dots that retain desirable electronic and optical
properties unaltered by high heat. Additionally, it would be an
advance in the art to provide new optical fiber structures and
materials that are compatible with quantum dots and with
conventional optical fibers.
SUMMARY OF THE INVENTION
[0008] The present invention includes a holey optical fiber having
a plurality of holes that provide light confinement. A plurality of
quantum dots are disposed within the holes. The quantum dots
provide wavelength conversion, amplification, fluorescence,
absorption, lasing and other linear and non-linear functions to the
fiber.
[0009] The fiber can be a regular or irregular array holey fiber, a
photonic crystal fiber, an index-guiding fiber, a random-hole holey
fiber, or combinations thereof, for example. The holes can be
disposed in the cladding, both the core and cladding, or a
plurality of cores and claddings with a plurality of geometric
cross-sections.
[0010] The quantum dots can be suspended in a solvent that is also
disposed in the holes. Alternatively, there is no solvent, and the
quantum dots re supported by sidewalls of the holes. The quantum
dots can preferably have diameters in the range of about 0.5-100
nanometers.
[0011] The present invention also includes an optical fiber made of
glass having a drawing temperature less than 700 Celsius, and
having quantum dots embedded in the glass. The glass can be a
phosphate glass or a lead glass (e.g. comprising more than 40%
phosphate or lead). The glass may also have a drawing temperature
less than 500 Celsius.
[0012] The quantum dots can be disposed in the core, the cladding
or both.
[0013] The present invention also includes a method for making
holey optical fibers with quantum dots disposed in the holes. In
the present method, the holey optical fiber is submerged in a
colloid or suspension of quantum dots in a solvent. The quantum
dots are drawn into the holes by capillary action. A cut end of the
holey fiber may be submerged in the quantum dot colloid.
DESCRIPTION OF THE FIGURES
[0014] FIG. 1 shows a cross sectional view of a random hole holey
fiber with quantum dots according to the present invention.
[0015] FIG. 2 shows a photonic crystal holey fiber with quantum
dots according to the present invention.
[0016] FIG. 3 shows a random hole holey fiber with holes in the
core containing quantum dots according to the present
invention.
[0017] FIG. 4 shows an index-guiding holey fiber containing quantum
dos according to the present invention.
[0018] FIG. 5 shows a generalized fiber sensor according to the
present invention.
[0019] FIG. 6 shows a random hole holey fiber with the holes
exposed to the environment. Exposed holes tend to increase sensor
sensitivity, particularly in chemical sensing applications.
[0020] FIG. 7 illustrates a preferred method for making the present
quantum dot optical fibers.
[0021] FIG. 8 shows a solid optical fiber having embedded quantum
dots, and made of a low melting point glass.
[0022] FIG. 9 illustrates a method for making random hole holey
optical fiber.
[0023] FIG. 10 shows a holey optical fiber with quantum dots
according to the present invention fusion-spliced to a conventional
solid fiber.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE
INVENTION
[0024] The present invention provides optical fibers having quantum
dots. The fibers are holey fibers and can be photonic fibers, index
guiding holey fibers, or random-hole holey fibers. In the present
invention, the quantum dots are incorporated into the holes of the
holey fibers. The holes can be in the cladding or core of the
fiber. Even if the quantum dots are disposed in the cladding, where
core-confined light exists as an evanescent wave, the quantum dots
interact strongly with guided light and can provide amplification,
sensing and other functions. The quantum dots can be inserted into
the fiber by flowing a colloid or suspension of the quantum dots
into the holes of the fiber. The colloid can flow under the
influence of capillary forces or via other entrainment methods such
as vacuum, thermal or mechanical means, and/or combinations of such
means. Retention of the quantum dots may be accomplished by
capillary force, splicing to conventional optical fibers, or
conversion of the solvent to solid or gelatinous forms, for
example.
[0025] In an alternative embodiment, the fibers can be made of low
melting point glasses (e.g., lead glasses, phosphate glasses)
having a working temperature (suitable for fiber drawing) less than
700C, 600C or 500C Many quantum dot materials can survive
temperatures in the range of about 400-700C.
[0026] FIG. 1 shows a cross section of a random-hole holey fiber
with quantum dots according to the present invention. The fiber has
a solid core 20 surrounded by a cladding 22 containing a large
number of randomly arranged holes 26. A solid sheath 24 surrounds
the cladding 22. In the present invention, quantum dots 28 are
disposed within the holes 26. The quantum dots are illustrated as
small rectangles or dots.
[0027] The fiber can be made of silica, alumina (sapphire),
ceramics, borosilicate glass, polymers, plastics or any other known
fiber material.
[0028] The random holes 26 can have diameters in the range of tens
of microns to less than a micron. The random holes can have lengths
of millimeters, meters or kilometers, for example. Preferably there
are hundreds of random holes in the fiber. Total required hole
cross-sectional area relative to the rest of the fiber is dependent
on the specific application or effect to be generated. The random
hole fiber can be made by preform methods such as sol-gel
processes, glass foam processes or by incorporating a gas
generating material into a glass fiber perform (as examples), and
then drawing the fiber from the resulting preform. FIG. 9
illustrates a method for making random-hole optical fiber based on
the latter technique as an example. In the method, a fiber preform
comprises a silica tube 50 filled with a holey region forming
powder 52 and a solid silica rod 54. The holey region forming
powder 52 forms a fiber cladding and the solid rod 54 forms a fiber
core. Heaters 56 heat the preform so that it can be pulled to form
a fiber 58, as known in the art.
[0029] The holey region forming powder 52 preferably comprises a
mixture of a glass material (e.g., high purity silica powder) and a
gas-generating material (e.g., silicon nitride). The gas generating
material produces a gas when heated above the sintering temperature
of the glass material. The gas generating material can produce gas
by thermal decomposition or by chemical reactions (e.g., oxidation)
with other components of the holey region forming powder, for
example. The gas generated within the holey region forming powder
52 forms trapped bubbles 60 as the holey region forming powder 52
sinters and softens. The bubbles 60 are stretched and drawn into
elongated tubes 62 as the fiber 58 is pulled. In preferred
embodiments, the glass material is silica, and the gas generating
material is a nitride or carbide ceramic. Alternatively, the gas
generating material can be a metal nitrate or metal carbonate (e.g.
sodium nitrate or sodium carbonate). If silicon nitride is used as
the gas generating material, it can be added in amounts of about
0.01-0.5% by weight. The method for making random hole fibers is
also described in the paper "Microstructural Analysis of Random
Hole Optical Fibers" by Pickrell et al., IEEE Photonics technology
Letters, Vol. 16, No. 2, February 2004, which is hereby
incorporated by reference.
[0030] The quantum dots 28 can be made of many materials including
2-6 and 3-5 compound semiconductors, tertiary compound
semiconductors, germanium, silicon, ceramics, dielectrics, metals
and the like as in known in the art. Specific examples of possible
materials for the quantum dots include ZnS, ZnSe, ZnTe, ZnO, CdS,
CdSe, CdTe, CdO, HgS, HgSe, HgTe, HgO, MgS, MgSe, MgTe, MgO, CaS,
CaSe, CaTe, CaO, SrS, SrSe, SrTe, SrO, BaS, BaSe, BaTe, BaO, AlN,
AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb PbS,
PbSe, PbTe, PbO and mixtures thereof. Cadmium selenide is
particularly useful because it has desirable optical properties
such as fluorescence and light amplification in the visible to near
infrared optical spectrum. Quantum dots may be combinations of the
foregoing materials and may include core-only configurations or
combined in core-shell configurations with polymer or non-polymeric
shells. Shell materials can range from polymers such as Trioctyl
Phosphine Oxide (TOPO) to non-polymeric such as ZnS as are known in
the art.
[0031] The quantum dots can have diameters typically between 1 and
10 nm or 1 and 100 nanometers. The size of the dots will depend
upon the application of the present optical fiber, the quantum dot
configuration (i.e., core only, core shell, etc.) and the
wavelength range to be addressed. A plurality of dot sizes may be
employed to achieve arbitrary wavelength spectral effects as
appropriate to the nature of the quantum dot materials. A
wavelength range from 0.3 microns to beyond 2 microns is
addressable in the optical fibers disclosed herein.
[0032] The quantum dots can be suspended in a liquid solvent within
the holes 26. The solvent can be toluene, heptane, chloroform,
xylene, acetone, hydrocarbon alcohols or the like. The quantum dots
can be freely floating in the solvent, or can be supported by the
sidewalls of the holes 26 (e.g., by Van der Waals forces). As
noted, the quantum dots can be coated with a capping material such
as TOPO, as known in the art, or can be uncoated (i.e. bare).
Further, the quantum dot structure may include other molecular or
atomic attachments such as chemicalibiological ligands, functional
molecules, etc. as are known in the art.
[0033] Compatible solvents may have an index of refraction greater
or less than that of the optical fiber material into which they are
entrained, depending on the functional effect to be achieved in the
over-all optical fiber structure. Preferably, however, the solvent
has a refractive index lower than the refractive index of the
glass. As an example, quantum dots arranged in a high index solvent
may enable total core confinement in random fiber core structures.
Further, solvents may be used that transition to a solid state with
processing or catalysis. As an example, low viscosity polymeric
adhesives that transition to a solid state on exposure to UV or
other wavelengths of light may be used.
[0034] FIG. 10 shows one embodiment of the invention including a
holey optical fiber with quantum dots 28 in holes 26, where the
holey optical fiber is fusion-spliced at joint 74 to a conventional
solid fiber composed of core 70 and 72. This embodiment
demonstrates use of the holey optical fiber in conjunction with
other fibers, as may occur in some sensor applications, etc.
[0035] FIG. 2 shows another embodiment of the invention having a
photonic holey fiber. Photonic holey fibers are well known in the
art. Photonic holey fibers have a regular array pattern of holes
26. The photonic holey fiber is typically made by stacking a bundle
of hollow glass tubes to form a fiber preform, and then drawing the
preform into a fiber. In the photonic holey fiber of FIG. 2,
quantum dots 28 are disposed within the holes 26 comprising the
photonic crystal lattice. The quantum dots can be suspended in a
solvent or supported on the sidewalls of the holes 26. Sidewall
attachment may be augmented with prior processing steps in which
the wall material is treated to enhance quantum dot attachment via
chemical or atomic bonding between the wall or wall impregnated
materials and the quantum dot structure.
[0036] Quantum dot concentrations may vary substantially depending
on the application, strength of light coupling in the materials and
the interaction length to be employed. As examples, a filter may
employ quantum dot concentrations less than 1% by volume, where
lasing applications typically require concentrations of greater
than 0.2% and prefer concentrations of greater than 1% by volume.
Concentrations in coherent applications are also dependent on the
diameter and length of the micro-cavities formed by the entrained
holes. Smaller diameters (e.g. less than 20 um), for instance,
enhance micro-cavity effects (e.g. lasing) for lower concentrations
of quantum dots.
[0037] In operation, the quantum dots interact with light traveling
through the core 20 of the fiber. The interaction can result in
light amplification, fluorescence, wavelength-shifting, nonlinear
optical effects, or environmental sensing (including radiation
fields from nuclear or cosmic bombardment). Although the quantum
dots are located within the holes 26, where light might exist only
as an evanescent wave, the quantum dots are able to interact with
light in the core and provide their effects. It is noted that the
quantum dots can interact with light propagating in the core by
coherent and/or incoherent scattering coupling mechanisms.
[0038] For example, in one experiment performed by the present
inventors, a photonic holey fiber like the fiber of FIG. 2 has
holes filled with a colloid of CdSe quantum dots in heptane (e.g.
with a volume concentration of 0.2% or more). When 488 nm pump
radiation is injected into the fiber core, a co-propagating 594 nm
signal beam traveling through the core experiences a power gain of
100% over a distance of 10 cm from evanescent field coupling of
both pump and signal to the quantum dots. The CdSe quantum dots
absorb the 488 nm energy and provide optical amplification at 594
nm. The quantum dot materials had been held in the experimental
fiber for in excess of a year via capillary forces alone.
[0039] It is noted that random hole holey fibers are particularly
well suited for use with quantum dots according to the invention.
Specifically, this is because random hole holey fibers tend to have
some holes that extend to the core region of the optical fiber,
where light intensity is greatest. As a result, the quantum dots
located close to the core interact strongly with core-confined
light.
[0040] FIG. 3 shows another embodiment of the present invention in
which the core 20 includes holes 30. The core holes 30 may contain
quantum dots. The core 20 in this embodiment has a lower porosity
than the cladding 22 so that light is confined to the core 20. The
fiber of FIG. 3 can be a random hole holey fiber made from a
preform having gas generating material incorporated into the core
and/or cladding region of the preform. An advantage of having core
holes 30 with quantum dots is that the quantum dots are located in
a region of high light intensity (even if they are exposed to only
an evanescent wave), and so will interact strongly with light
across the core 20.
[0041] FIG. 4 shows an embodiment of the invention in which the
holey optical fiber is an index-guiding holey fiber, as known in
the art. In this case, the optical fiber does not have a regular
crystalline pattern of holes like the fiber of FIG. 2. In the
present invention, Quantum dots 28 are disposed within the holes 26
of the index-guiding holey fiber. Methods for making index-guiding
and photonic crystal holey fibers are well known in the art.
Typically, solid rods and hollow tubes are stacked to form a fiber
perform, which is then heated and drawn into a thin fiber. U.S.
Pat. No. 5,155,792 to Vali et al. and U.S. Pat. No. 5,802,236 to
DiGiovanni et al. describe methods for making microstructured
optical fibers, and are hereby incorporated by reference in their
entirety.
[0042] As is well known in the art, in conventional optical fibers,
the microstructure of the fiber consists of a core region
surrounded by a clad region. Holey fibers generally consist of a
more complex mixture of core(s) and clad regions with interspersed
holes, the totality of which is referred to herein as the fiber's
microstructure. In conventional optical fibers, the core of the
fiber has a higher index of refraction than the clad region leading
to light guiding in the core via total internal reflection due to
the index difference as noted. In this sense, the guiding region of
the fiber is comprised of essentially the core. In holey fibers
entrained with quantum dot bearing solvents, the index of the
solvent relative to the index of the surrounding microstructure
determines the guiding region or regions. For example, if the index
of the solvent is uniformly lower than that of the glass
microstructure in a uniform index glass holey fiber, the entire
glass microstructure becomes the guiding region. If the index of
the solvent is higher than the glass in this example, the solvent
containing regions would become the guiding region. The guiding
region would include or exclude the region conventionally
designated as the core(s) of the microstructure on the basis of the
index difference. Depending on microstructure details, quantum dot
holey fibers may use any portion of the total microstructure as the
guiding region.
[0043] The present quantum dot holey fibers can be used in a wide
range of sensing applications. Quantum dots have electronic
structures and optical properties that respond to a variety of
chemical and physical environmental changes. For example, the
present fibers can be used in pH and chemical sensors, pressure or
force sensors, electric field sensors, magnetic field sensors, and
temperatures sensors. Typically, sensors based on the present
quantum dot holey fibers will operate to detect an optical
characteristic such as a shift in fluorescence, lasing or
absorption wavelength or intensity of the quantum dots. Such
effects may arise from linear or non-linear optical properties.
FIG. 5 shows a generalized fiber sensor according to the present
invention. The sensor has a holey fiber 32 containing quantum dots.
The fiber is connected to a light emitter and an optical detector.
The light emitter can produce single wavelengths or a broad
spectrum of wavelengths. The optical detector detects changes in
absorption, lasing or fluorescence in the optical fiber caused by
interactions of the quantum dots with the environment. The optical
detector can be a spectrophotometer, for example.
[0044] If the index of the solvent is lower than that of the glass
material, light may be guided by, and therefore confined to either
the region around the holes represented by the core or the region
surrounding holes represented by the cladding structure. If the
fiber is coated with a low index coating instead of the high index
clad typically used to strip off cladding modes, the cladding mode
light will form effective light for sensor operations. This concept
is very useful for all kinds of sensors, in that it preserves light
for signal to noise ratio enhancements and preserves a larger
fraction of the fiber sensor's cross-section for interaction with
the environment.
[0045] Also, it is noted that in the sensor embodiments, the
solvent can have a higher or lower refractive index than the
glass.
[0046] Following is a list of considerations for making different
types of sensors:
[0047] pH sensor: In a pH sensor according to the present
invention, quantum dots are selected that change optical properties
when exposed to H+ ions or OH- ions. Examples of such quantum dots
include the CdSe/ZnS core-shell dots which have been used for proof
of principle tests. In use, the fiber is submerged in a liquid to
detect the pH. H+ ions diffuse through the glass and come in
contact with the quantum dots, thereby affecting their
fluorescence, absorption, lasing or other optical characteristics.
To enhance the sensitivity, and make the fiber capable of sensing
species that cannot diffuse through glass (e.g., OH-), the fiber
can be designed to lack the solid sheath 24. The solid sheath 24
can be removed by etching, or the fiber can be drawn without the
solid sheath. Such a fiber is illustrated in FIG. 6.
[0048] Chemical/Biological sensor(s): In a chemical, biological, or
bio-chemical sensor, the quantum dots can be chemically bound or
essentially "coated" with a material (e.g. a polymer, biological
material, ceramic or metal) that changes the optical properties of
the quantum dot when it comes in contact with a chemical to be
detected. For example DNA ligands or bio-hazard molecules. In this
case, the species or element to be detected can be injected or
diffused into the holes 26, via molecular diffusion, capillary
action or other means appropriate to the state and structure of the
fiber-quantum dot sensor. Alternatively, the fiber can be processed
(e.g. chemically etched, mechanically abraded or cut open) so that
the holes are opened to the outside world and the chemical to be
detected can flow into the holes 26 again via molecular diffusion,
capillary action or other means appropriate to the state and
structure of the fiber-quantum dot sensor. For example,
biomolecules dissolved or dispersed in water can be detected by
submerging a cut fiber end in the water, and allowing the
biomolecules to diffuse into the holes. One advantage to this
technique is that the requisite amount of sample for analysis is in
the range of nano to microliters. This allows analyte solutions to
remain essentially undiminished in volume.
[0049] Force/strain sensor: Quantum dots supported or adhered to
the sidewalls of the holes 26 are sensitive to the electronic state
or atomic energy states of the sidewall. This is particularly true
if the quantum dot lacks a coating (e.g. TOPO) or the coating of
the quantum dot and wall are chosen to enhance any surface energy
interactions. As a result of interactions between the quantum dots
and sidewall energy states, the electronic structure and optical
properties of the quantum dots will be altered by strain in the
fiber material matrix. Hence, the strain or force can be detected
by monitoring the optical characteristics of the quantum dots.
Wavelength shifts up to 15 nm are readily observed between the
fluorescent emission peaks of bulk CDSe/ZnS quantum dot-heptane
colloids in a beaker and the same material entrained in holey fiber
structures with a plurality of 6-14 um diameter holes. Wavelength
shifts (35 nm) are likewise noted down the length of such fibers
due to emission/re-absorption/filtering effects that may be
modulated with micro-bending of the optical fiber.
[0050] Electric field/magnetic field sensor: it is well known that
the electronic structure and optical properties of quantum dots can
be altered by electric or magnetic fields. Electric and magnetic
fields can be detected by monitoring changes in absorption, lasing,
fluorescence or other characteristics of the quantum dots.
[0051] X-ray, Nuclear radiation or particle detection: it is well
known that the electronic structure and optical properties of
quantum dots can be altered by encountering X-ray/nuclear radiation
or high energy particles. In particular, such encounters can
generate direct fluorescent light generation or cause degeneration
of the quantum dot material with attendant effects on the materials
optical properties. Consequently, quantum dot loaded optical fibers
can be used to develop a variety of sensors for direct or remote
sensing of radiation parameters.
[0052] Wavelength conversion sensors and fibers: Use of embedded
quantum dots in a cascade of response characteristics from shorter
wavelengths to longer wavelengths enables the use of conventional
detectors and filter elements sensitive to longer wavelengths for
sensing short wavelength radiation. Such wavelength conversion
could be enabled by the ordinary absorption/emission
characteristics of the quantum dots or higher level optical
properties such as Brillioun and Raman scattering. For example, a
holey fiber embedded with quantum dots which absorb at UV
wavelengths below 350 nm and re-emit at wavelengths above 400 nm
may be used with conventional silicon detectors instead of the less
sensitive, more expensive extended response silicon detectors.
Longer wavelength filter elements may also be used in this
technique to enhance signal to noise ratio or other signal
properties. Similarly, a mixture of quantum dots in varying sizes
may broaden the absorption and emission band to allow detection of
X-ray or nuclear radiation by conventional silicon detectors in
replacement of conventional scintillation detectors. In each case,
some portion of the light absorbed by the quantum dots is emitted
at longer wavelengths to be sensed and/or filtered by detectors and
filters whose performance characteristics peak at the longer
wavelengths.
[0053] FIG. 7 illustrates a method for making the present quantum
dot holey fibers. In the preferred method, a cut end 36 of a holey
optical fiber is submerged in a colloid or suspension of quantum
dots in a solvent. Alternatively, a sidewall of the fiber is
etched, abraded or otherwise cut open to expose some of the holes
26, and the sidewall with exposed holes is submerged. Under the
influence of capillary forces, the solvent is drawn into the holes
of the holey fiber. The solvent can be heptane, xylene, or other
hydrocarbons or alcohols, for example. Depending on hole size,
solvent combinations and capillary assist methodology the colloid
can travel millimeters to kilometers into the holey fiber. High
vapor pressure solvents (low viscosity) will generally travel
further into the optical fiber than low vapor pressure solvents. If
the holes are too small (e.g. submicron size) some solvents might
not be drawn into the holes without assistance. The hole size
should be selected in view of the solvent to be used, the surface
properties of the holes, and the desired distance for the quantum
dots to be drawn into the fiber and the desired optical effect.
[0054] Capillary forces can result in long duration containment of
the quantum dots. Capillary forces have been demonstrated to hold
entrained quantum dots for storage times in excessive of two years
in proof of principle experiments. Also, the ends of the fiber can
be fused or melted (e.g. with a fusion splicer) so that the holes
are sealed shut at the ends. Further the holey fiber can be fused
to solid fibers both for sealing and connection into conventional
fiber networks.
[0055] Optionally, the solvent can be removed (e.g., by vacuum
evaporation) after the quantum dots have been inserted into the
fiber. Also, the fiber can be submerged for a short duration (e.g.,
less than 1 second) so that the quantum dot colloid only travels a
short distance. The resulting holey fiber with localized quantum
dot distribution can be used as a sensor with localized
sensitivity, for example. Quantum dot penetration may alternately
be limited via other means, including mechanically induced
blockages, splicing to solid element fibers and other methods as
are obvious to those skilled in the state of the art.
[0056] FIG. 8 shows another embodiment of the invention in which
the optical fiber is solid glass and contains embedded quantum
dots. The fiber has a cladding region 42 and a core 44. The core 44
and cladding 42 both contain quantum dots 28. Alternatively, only
the cladding or core contains quantum dots. Significantly, the
fiber is made of a low-melting point glass that can be drawn into a
fiber at temperatures that do not damage the quantum dots 28. For
example, the fiber can be made of phosphate glasses (e.g. at least
25% phosphate), lead glasses or chalcogenide polymers, which can be
drawn into a fiber at temperatures in the range of 300-700 degrees
Celcius. Preferably, the fiber is made of a glass that can be drawn
at a temperature less than 700C, 600C, 500C or 400C. The sheath,
cladding and core can all be made of the same glass. The core 44
should have a dopant or slightly different composition so that it
has a higher refractive index than the cladding, as well known in
the art.
[0057] Of course, the quantum dots used must be resistant to the
temperatures used to draw the optical fiber. Examples of suitable,
heat-resistant quantum dot materials include tellurides, antimonies
and CdSe since it has a boiling point between 600 and 700 degrees C
(depending on confinement conditions). In general, the quantum dot
material should have a boiling point lower than the drawing
temperature of the glass.
[0058] The optical fiber of FIG. 8 can be made by incorporating
quantum dots into a fiber preform, and then drawing the fiber
preform into an optical fiber. The fiber preform can comprise glass
powder mixed with quantum dot materials, such as a quantum dot
colloid or suspension as is common in the art with the technique
known as solution doping (an extrinsic doping process). In this
technique, a glass frit or power is deposited internal to a preform
tube via chemical deposition or other means. The quantum dot
bearing solvent is then placed in the preform in sufficient volume
to allow the solvent to be entrained into the porous interior
surface. After residual solvent is removed, the preform is
collapsed and drawn into a fiber as is common in the art. In an
alternate embodiment of this technique, the powder material may be
impregnated with or bound to the quantum dot-solvent materials and
then deposited in the preform as a slurry material). In this regard
an extrinsic process is defined as one in which the quantum dots
have been formed in a separate process prior to embedding in a
final host material. By contrast an intrinsic process would form
the quantum dots from their constituent materials during
processing. For example if Cd and Se elements were used to dope a
glass preform and the preform processed in such a manner that the
CdSe quantum dots form on cooling an intrinsic process would be
formed.
[0059] The optical fiber of FIG. 8 can be used for many
applications such as light amplification, wavelength shifting,
saturable absorption, and sensing in accordance with the nature of
the structure and materials used. For example, the fiber of FIG. 8
with embedded quantum dots can be used as a force or strain sensor
since the quantum dots will be affected by strain on the fiber.
[0060] It will be clear to one skilled in the art that the above
embodiment may be altered in many ways without departing from the
scope of the invention. Accordingly, the scope of the invention
should be determined by the following claims and their legal
equivalents.
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