The present invention relates to the fabrication of wires having a diameter of the order of nanometres.
This application claim priority from the following Australian Provisional Patent Applications:
2005905619 entitled “Fabrication of Nanowires” filed on 12 Oct. 2005; and 2005905620 entitled “Method and Device for Forming Microstructured Fibre” filed on 12 Oct. 2005.
The entire content of each of these applications is hereby incorporated by reference.
“Nonlinearity enhancement of filled microstructured fibres operating in the nanowire regime”, K. J. Rowland, Shahraam Afshar V, T. M. Monroe; Optical
Fiber Communication Conference (OFC'2006), Anaheim 5-10 Mar. 2006, Paper OThH4, 2006.
The entire content of this publication is hereby incorporated by reference.
Nanowires are wires having diameters ranging up to several hundred nanometres. Nanowires are extremely sensitive to their surroundings and so are suited to a plethora of sensing applications. The fibre geometry provides extremely long optical path lengths and allows the use of small sample volumes.
Nanowires work by detecting changes in light, whereby the nanowire functions as a “rail” for the light since most of the light is situated in the surrounding cladding comprising holes filled with air or fluid, and thus the light can interact with any materials (gases, liquids, particles, etc) in the holes. Changes in the properties of the mode field of the light due to interaction with the material will be transmitted along the nanowire and can be detected at the output end of the nanowire device.
A nanowire has enhanced sensitivity compared with wires of larger diameter, since the power fraction of light in the environment is much larger for nanowires than for wires of larger diameter. The larger power fraction of light in the fluid surrounding the nanowires results in larger overlap of light and fluid, resulting in the enhanced sensitivity of nanowires.
Nanowires are however, difficult to fabricate. The fabrication of nanowires in the laboratory is a process which requires considerable skill, particularly since it is desirable to produce a wire in which the diameter does not fluctuate substantially over the length of the wire and the sidewall roughness is kept to a minimum. Diameter fluctuations, sidewall roughness and contamination can make the wires unsuitable for low loss optical wave guiding.
In order to have broad ranging commercial application, it is desirable that nanowires are of a sufficient length for practical use. For, example, the wires may be required as sensors, embedded into a structure having dimensions of the order of meters. However, known techniques for the fabrication of nanowires result in very short portions of wire, which are of scientific interest but have limited commercial viability.
One known technique for the formation of nanowires includes a two step drawing process. The first step involves the use of a flame to draw a silica fibre to micrometer-diameter wire. Secondly, one end of the drawn wire is placed horizontally onto a tapered tip (usually a sapphire fibre taper) and the tip is rotated about its axis to wind the silica nanowires. Using this technique, nanowires with diameters smaller than 50 nm can be obtained, however, the lengths of wires produced are only of the order of tens of millimetres. A problem anticipated for longer nanowires is that while they are extremely sensitive to their surroundings, they are fragile and prone to contamination during handling. One way of supporting a nanowire is to encase the wire in a porous substance such as an aerogel. This allows the wire to be handled, however, the disadvantage is that the arrangement is no longer flexible, which limits the commercial application as well as the ability to act as a sensor.
Nevertheless, a nanowire which is fully enclosed within a supporting structure loses the ability to perform point detection since the core may not be close enough to the surface walls.
It is an object of the present invention to address at least one of the problems discussed above.
According to one aspect of the present invention, there is provided a method of forming a fibre incorporating a nanowire, the method comprising:
In one form, the primary preform is formed by extrusion.
In one aspect, the outer portion is formed to provide a space leading to the cane receiving portion.
In one form, the space is a wedge-shaped cut-away in the outer portion.
In another form, the method further comprises etching away at least a part of the support structure that is exposed to the space to expose the nanowire.
In one form, the primary preform is made from a soft glass.
In one aspect of this, the soft glass is lead silicate.
In another form, the primary preform is made from a polymer.
According to another aspect of the present invention, there is provided a fibre containing a nanowire, the fibre comprising:
In one form, the fibre further comprises at least one cladding region surrounding the nanowire.
In one form, the support structure comprises at least one strut extending radially from the central portion.
In one aspect, the at least one strut terminates at a wall portion forming a perimeter of the support structure.
In another aspect, the support structure comprises four struts extending radially from the central portion.
In one form, the wall portion defines a square in cross-section.
In one aspect, the outer portion comprises a cut-out for providing access to a part of the wall portion.
In another aspect, the wall portion defines three sides of a square in cross-section.
In one form, the cut-out is wedge-shaped.
According to another aspect of the present invention, there is provided a method of forming a nanowire, the method comprising:
In one form, the step of forming the preform structure comprises inserting the central portion and the support structure into the outer portion.
In another form, the step of forming the preform structure comprises extruding the preform structure.
In one aspect, the method further comprises forming the central portion and the support structure by drawing a primary preform structure.
In another aspect, the method further comprises forming the primary preform structure by extrusion.
According to another aspect of the present invention, there is provided a nanowire formed according to the method of any one of the preceding methods.
According to another aspect of the present invention, there is provided a preform for forming a fibre containing a nanowire, the preform comprising:
In one form, the support structure comprises at least one strut extending radially from the central portion.
In one form, the at least one strut terminates at a wall portion forming a perimeter of the support structure.
In another form, the support structure comprises four struts extending radially from the central portion.
In one form, the wall portion defines a square in cross-section.
In one form, the outer portion comprises a cut-out for providing access to a part of the wall portion.
In one form, the cut-out is wedge-shaped.
In another form, the four struts terminate in respective corners of the wall portion.
According to another aspect of the present invention, there is provided a method of forming a nanowire, the method comprising drawing a cane having a central portion supported by a support structure until the central portion is a nanowire.
According to another aspect of the present invention, there is provided a method of increasing the nonlinearity of a nanowire, the method comprising surrounding the nanowire with a nonlinear fluid.
In one form, the nanowire is surrounded by a support structure and an outer portion, defining at least one channel in fluid communication with the nanowire, the step of surrounding the nanowire with the nonlinear fluid comprising introducing the nonlinear fluid into the at least one channel.
In one form, the nonlinear fluid is carbon disulphide.
According to a further aspect of the present invention, there is provided a fibre incorporating a nanowire, formed by the method according to any one of the preceding methods.
According to a further aspect of the present invention, there is provided a sensor comprising the fibre according to any one of the preceding aspects of the invention for sensing at least one parameter of, an environment existing within the at least one cladding region.
According to a further aspect of the present invention, there is provided a method of forming a fibre incorporating a plurality of nanowires, the method comprising:
In one form, the primary preform is formed by extrusion.
In one form, the outer portion is formed to provide a space leading to the cane receiving' portion.
In one form, the space is a wedge-shaped cut-away in the outer portion.
In one form, the method further comprises etching away at least a part of the support structure that is exposed to the space to expose at least one of the nanowires.
In one form, the primary preform is made from a soft glass.
In one aspect, the soft glass is lead silicate.
In another form, the primary preform is made from a polymer.
According to another aspect of the present invention, there is provided a fibre containing a plurality of nanowires, the fibre made by the method of the previous aspect of the present invention.
In one form, the number of nanowires is 2.
In another form, the number of nanowires is 3.
According to a further aspect of the present invention, there is provided a nanowire greater than 10 mm in length.
In one form, the nanowire is about 1 km in length.
In another form, the nanowire is about 10 km in length.
Throughout this specification unless the context requires otherwise, the words ‘comprise’ and ‘include’ and variations such as ‘comprising’ and ‘including’ will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers.
The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that such prior art forms part of the common general knowledge.
A specific embodiment of the invention will now be described in some further detail with reference to and as illustrated in the accompanying figures. This embodiment is illustrative, and is not meant to be restrictive of the scope of the invention. Suggestions and descriptions of other embodiments may be included within the scope of the invention but they may not be illustrated in the accompanying figures or alternatively features of the invention may be shown in the figures but not described in the specification.
An embodiment of the invention is illustrated in the accompanying representation in which:
FIG. 1A—is a cross-sectional view of a primary preform for use in the present invention;
FIG. 1B—is a cross-sectional view of an alternative form of the primary preform of
FIG. 1C—is a perspective view of the primary preform of
FIG. 2—is a perspective view of a cane resulting from the primary preform of
FIG. 3A—is a cross-sectional view of an alternative structure of the primary preform of
FIG. 3B—is a cross-sectional view of an alternative structure of the primary preform of
FIG. 3C—is a cross-sectional view of an alternative structure of the primary preform, having three central portions;
FIG. 3D—is a cross-sectional view of an alternative structure of the primary preform, having four central portions;
FIG. 4A—is a cross-sectional view of the outer portion or cane jacket for use in the present invention;
FIG. 4B—is a perspective view of the outer portion or cane jacket of
FIG. 5—is a perspective view of the secondary preform for use in the present invention;
FIG. 6—shows the completed fibre containing the nanowire according to an aspect of the present invention, showing various magnifications;
FIG. 7A—shows the completed fibre of
FIG. 7B—shows the completed fibre of
FIG. 8—shows a flowchart of one method of forming a nanowire according to an aspect of the present invention; and
FIG. 9—shows a flowchart of another method of forming a nanowire according to another aspect of the present invention.
In accordance with one aspect of the present invention, a primary preform is first formed with the required structures therein.
In one form, primary preform 10 is formed by extruding a billet of suitable material through a suitably designed die. Suitable materials for forming the primary preform include polymers and soft glasses such as fluoride, heavy metal oxides, chalcogenides and other glass types. In one particular embodiment, the material is soft glass such as lead silicate which is passed through the die at a temperature of 520° C. and a fixed ram speed of 0.2 mm./min.
In other forms of the invention, primary preform 10 may be formed by other methods including moulding, casting, drilling stacking or even manual assembly.
The width of primary preform in
Similarly, the diameter of the central portion 16 can vary as desired, and in one example is about 2 mm.
A suitable die and extrusion method are detailed in a co-pending application entitled: “Method and device for forming micro-structured fibre”, claiming priority from Australian provisional patent application no. 2005905620 filed on 12 Oct. 2005, the entire contents of which are hereby incorporated by reference.
It will be appreciated that any number of struts as is practicable could be disposed within primary preform 10. For example, three struts could be used instead of four. In fact, the number of struts could be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more. Furthermore, the primary preform need not have a square shaped cross-section but instead could be any desired shape. For example, the cross-section may be circular, triangular, rectangular, pentagonal, hexagonal, heptagonal, octagonal etc, or be of an irregular shape. It is also an option that the struts are shaped differently to those illustrated in
Once formed, primary preform 10 is then reduced in scale in a drawing tower, to form a cane 20 as shown in
As previously described, it is also an option that the primary preform 10 has two (or more) central portions 16a and 16b (for example, with each central portion offset from the geometrical centre of the primary preform 10 but forming the centre of an independent strut structure).
An advantage of having more than one central portion is that multiple central portions allow the formation of multiple nanowires (described in more detail further below). Each nanowire can then be used either as an independent sensor or as coupled sensors and if desired, each nanowire sensor could have different spectral characteristics. Alternatively, one nanowire could serve as a rail for light in one direction and the other nanowire could serve as a return rail for the light.
Cane jacket 22 has a cane receiving portion 24 which forms a longitudinal channel running along the longitudinal axis of the cane jacket. This longitudinal channel is more clearly shown in
Cane receiving portion 24 is disposed within a space, which in one embodiment, is a wedge shaped cut-away 26. The wedge shaped cut-away allows cane 20 to be manually inserted in the jacket, thereby forming a preform assembly, or secondary preform 28 as shown in
It is an option that a structure similar to preform assembly 28 is prepared as one integral preform, rather than being formed from two separately prepared parts which are subsequently joined as has been described above. However, given that the dimensions of cane 20 are relatively small (i.e. width of cane is 1 mm) it is preferable to draw the cane from a macroscopic primary preform since this ensures that the dimensions remain consistent along the length of the cane. Nevertheless, complicated structures providing an integral cane and cane jacket may be obtained through extrusion for example, using a die such as that described in the previously incorporated reference entitled “Method and Device for Forming Microstructured Fibre”
As outlined above, it is also an option that primary preform 10 has a cross-section other than a square cross-section. In this case, cane receiving portion 24 of jacket 22 would be of a corresponding shape so as to snugly fit cane 20 into the receiving portion. For example, if cane 20 had a circular cross-section, cane receiving portion of jacket 22 could be shaped as a semicircle. If cane 20 had a triangular, cane receiving portion could also be shaped as a triangle.
In one embodiment, the cane jacket has an outer diameter of about 23 mm and the cane receiving portion having an inner edge-to-edge length of about 1.3 mm. Again, any other suitable dimensions would be possible as would be understood by the person skilled in the art.
Once assembled, preform assembly or secondary preform 28 is drawn, in a drawing tower, in order to create a fibre 30 having a core 31 (
Nanowires produced according to the various aspects of the present invention are able to achieve lengths far greater than those currently achievable. The length of the nanowire produced in unitary form may range from tens of millimetres to hundreds of kilometres in length. For example, the nanowire may be 5 mm-10 mm, 1 cm-5 cm, 5 cm-10 cm,10 cm-20 cm, 20 cm-50 cm, 15 cm-75 cm, 50 cm-100 cm, 100 cm-250 cm, 200 cm-500 cm, 500 cm-1000 cm, 1 km-1.5 km, 2 km-5 km, 5 km-10 km, 10 km-50 km, 50 km-100 km, 100 km-200 km.
It should be understood that fibre 30 has substantially the same topology as preform assembly 28 however the cross-section dimensions are substantially reduced. Most importantly, the central portion 16 of primary preform 10 now has a width of the order of nanometres, thereby providing nanowire 32.
Nanowire 32 is supported by support structure or walls 12 which defines around the wire, cladding or air channels 18. In use, a substantial portion of guided light will be situated in the air channels 18 surrounding nanowire 32, the nanowire acting as a rail rather than a pipe for the light. The support structure 12 is further supported by jacket 22 which allows the nanowire 32 to be handled as a traditional fibre. The structural integrity provided to the nanowire by the outer jacket means that the problems of fragility and contamination which have posed difficulties for fabricated nanowires in the past are eliminated to a certain extent.
In
It is an option that the wedge shaped cutaway 26 has any shape which permits some access to the core 31 of fibre 30. For example, the cut-away portion of jacket 22 could be a groove, having sides which are substantially parallel to one another.
The exposed core fibre addresses the problem of having a supported nanowire which must compromise its sensitivity for the support. Instead, in this arrangement, the nanowire is both supported and sensitive since the core is as close to the surface as possible.
It should be appreciated that struts 14 may be disposed so that once a portion of support structure 12 is etched away, the entire core 31 of fibre 30 is not exposed e.g. one air channel 18 (see
It will of course also be understood that it is possible to perform the etching in such a way, that not only wall 34 but also the two struts at the end of wall 34 are totally or partly etched and thus the fluid to be sensed has access to three air channels. In this case, the core may only be supported by two struts, as shown in
It is also an option that cane 20 is prepared with one or more walls missing such that upon incorporation into jacket 22 the nanowire is exposed without the need for etching. The etching of a wall once the fibre is formed however, (as has been described above) reduces the exposure of the nanowire to the surrounding environment prior to use of the fibre thereby reducing contamination.
While not essential, it could be useful to have one or more “sealed” channels to allow the introduction and isolation of different fluids. This can be used to allow differential sensing between two different environments, or indeed use one of the channels to house a reference fluid to provide for internal referencing.
In application, the materials (gases, liquids, particles, etc) introduced into the channels may be used to increase the non-linearity of the sensor formed by the structure according to the various aspects of the present invention. In particular, the introduction of a non-linear fluid such as Carbon Disulphide (CS2) into the channels has been found to significantly enhance the effective nonlinear coefficient of soft glass nanowires and microstructured fibres with nanowire cores such as provided by the present invention.
This application is set out in more detail in the paper entitled “Nonlinearity of filled microstructured fibres operating in the nanowire regime” K. J. Rowland, Shahraam Afshar V, T. M. Monroe; Optical Fiber Communication Conference (OFC'2006), Anaheim 5-10 Mar. 2006, Paper OThH4, 2006 the entire contents of which are hereby incorporated by reference.
In other applications, useful information could be obtained by exciting one or more materials within the channels to cause them to emit energy (or fluoresce) into the nanowire itself, which can then be detected at an end of the nanowire/fibre structure and analysed.
It is also within the scope of the present invention to produce a nanowire by simply drawing the cane structure shown in
It is also within the scope of the present invention to form a completely exposed nanowire. This may be done in a number of ways including forming the enclosed nanowire according to the various aspects of the present invention, and etching or otherwise dissolving the outer portion or jacket and support structure to leave the internal nanowire exposed. In this case, the central portion can be constituted by a different material to the support structure and outer portion to facilitate the selective removing of the material around the nanowire. Alternatively, the support structure could be etched away completely to allow the outer portion and the nanowire to be separated.
Of course, if the nanowire is formed from simply drawing the cane, without the use of the outer portion (or cane jacket), as described above, it will be necessary only to dissolve the support structure to leave the completely exposed nanowire.
The resulting article is a fibre containing within it, a nanowire. An optional step is then shown as step 104 (dotted lines), in witch at least a portion of the fibre is etched away, or otherwise removed, to expose a portion of the nanowire for use in applications such as sensing. Of course it will be understood that in some applications such as optical communications for example, it may be desirable to leave the nanowire completely encased in the fibre, and therefore no etching or removal will be done. It may also be an option to completely remove the fibre to leave the nanowire entirely exposed for other applications as required.
It will also be understood that a particular party could perform one or more aspects of the invention at different stages. For example, one party could form the primary preform, another party could obtain the preformed primary preform from this party and draw it to a cane or directly to a fibre containing the nanowire, another party could obtain the cane and draw this to a fibre containing a nanowire, and a further party could then etch the fibre containing the nanowire as desired, depending upon the intended application.
It is intended that the present application cover all combinations of these methods.
The nanowires and fibres produced according to the various aspects of the invention have many applications, including, but not limited to sensors for use in scientific, medical, military/defence and commercial application; displays for electronic products such as computers, Personal Digital Assistants (PDAs), mobile telephones; image displays and sensors for cameras and camera phones; optical data storage; optical communications; optical data processing; traffic lights; engraving; and laser applications.
It will be appreciated by those skilled in the art that the invention is not restricted in its use to the particular application described. Neither is the present invention restricted in its preferred embodiment with regard to the particular elements and/or features described or depicted herein. It will be appreciated that various modifications can be made without departing from the principles of the invention.
Therefore, the invention should be understood to include all such modifications within its scope.
Number | Date | Country | Kind |
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2005-905619 | Oct 2005 | AU | national |
2005-905620 | Oct 2005 | AU | national |
This application is a divisional of pending U.S. patent application Ser. No. 12/089,986, filed Apr. 11, 2008, which is the National Stage of International Application No. PCT/AU2006/001501, filed Oct. 12, 2006, the disclosure of which is expressly incorporated herein by reference in its entirety. The International Application was published under PCT Article 21(2) in English.
Number | Date | Country | |
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Parent | 12089986 | Jul 2008 | US |
Child | 12914134 | US |