Optical Fiber Technology 16 (2010) 343356

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Optical Fiber Technology

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Invited Papers

Sensing with suspended-core optical bers

Tanya M. Monro , Stephen Warren-Smith, Erik P. Schartner, Alexandre Franois, Sabrina Heng, Heike Ebendorff-Heidepriem, Shahraam Afshar V
Institute for Photonics & Advanced Sensing (IPAS), School of Chemistry & Physics, The University of Adelaide, Adelaide SA 5005, Australia

a r t i c l e

i n f o

a b s t r a c t
The development of optical bers with suspended cores has enabled the demonstration of a range of powerful new techniques for chemical and biological sensing. Here the fabrication, design and application of this new class of bers are reviewed. The performance and potential of sensors based on these bers is evaluated, including dip sensors for sensing small sample volumes, exposed-core bers for real-time and distributed measurements, and surface functionalized bers for the specic detection of chemicals and biomolecules. 2010 Published by Elsevier Inc.

Article history: Received 30 August 2010 Revised 16 September 2010 Available online 27 October 2010 Keywords: Microstructured optical bers Nanowires Fiber sensing Chemical sensing Biological sensing Surface functionalization

1. Introduction Numerous applications in health, the environment, agriculture and national security require fast, sensitive and portable tools for the detection of specic chemicals and biomolecules. Most commercially available sensors rely on analytical methods that are too expensive, bulky or slow to fulll the requirement of a point of care or eldable device. The simplest way of using an optical ber for sensing it to use it to transport light to and from the sensing region. In such congurations, the interaction between the light and the environment such as scattering, absorption, and uorescence occurs externally to the ber. This class of sensor has been widely used to detect gases such as methane via the use of near-IR absorption spectra [1]. While this approach makes use of optical bers as a transport mechanism, such sensors do not take advantages that bers can offer when they are used as intrinsic sensors. Optical bers that incorporate air holes within their cross-section offer numerous new characteristics and opportunities for chemical and biological sensing [2]. The holes within microstructured optical bers (MOFs) can be used to control the interactions

Corresponding author at: Physics Building, The University of Adelaide, Adelaide, SA 5005, Australia Fax: +61 8 8303 4380. E-mail addresses: tanya.monro@adelaide.edu.au (T.M. Monro), stephen. warrensmith@adelaide.edu (S. Warren-Smith), erik.schartner@adelaide.edu.au (E.P. Schartner), alexandre.francois@adelaide.edu.au (A. Franois), sabrina.heng@ adelaide.edu.au (S. Heng), heike.ebendorff@adelaide.edu.au (H. Ebendorff-Heidepriem), shahraam.afshar@adelaide.edu.au (S. Afshar).
1068-5200/$ - see front matter 2010 Published by Elsevier Inc. doi:10.1016/j.yofte.2010.09.010

between guided light and matter located within the holes while simultaneously acting as tiny sample chambers. The rst optical bers containing holes within their cross-sections were reported in the 1970s as part of the drive to develop low loss bers for optical data transmission [3]. In these rst microstructured optical bers (MOFs), which were made from undoped silica glass, the ber core was effectively suspended in air within a robust solid jacket by a thin membrane of glass. Creating the ber cladding from air in this way enabled a single-mode ber to be fabricated from a single high purity low loss material. Due to the development of vapor deposition based techniques for low loss silica preform fabrication, little further research on microstructuring within ber cross-sections was performed until the mid 1990s, when interest in MOFs was re-awakened in 1996 with the rst demonstration of optical guidance within bers with a complex holey cladding structure [4]. This work was driven by the development in the late 1980s on photonic crystals [5], which identied wavelength-scale structuring to be a powerful means of modifying the transmission characteristics of optical materials, and ultimately led to the demonstration of air-guiding photonic bandgap bers [6]. The advent of MOFs has enabled signicant advances in a number of elds including nonlinear optics, optical data processing, ber lasers and sensing. The possibility of making ber claddings that range from being mostly comprised of air, to largely solid, enables a much broader range of numerical apertures than conventional bers. As a consequence, the effective transverse size of the guided mode can specied over a much broader range, allowing the production of bers with large effective mode areas for high

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power light transport and generation [7], or the tight connement of light for the production of strong nonlinear effects [8]. The presence of wavelength-scale transverse features (i.e. the holes) leads to novel properties such as endless single-mode guidance [9], and allows properties such as dispersion and birefringence to be tailored via choice of the ber cross-section [10]. The simple fact that MOFs can be fabricated from a single material also means that it is now possible to make optical bers from materials that were previously unavailable for this purpose due to the lack of suitable compatible cladding materials [11]. The development of new sensing platforms has been driven forward by two key classes of MOFs: bers with solid suspended cores and air-core photonic bandgap bers. Both classes of ber are attractive for sensing due to the signicant overlap they can offer between the guided mode of the ber and the air holes within the cross-section. The focus of this paper is to review recent advances in suspended-core bers, which serve as a versatile platform for interacting light with liquids for numerous applications in biological and chemical sensing. 2. Suspended-core bers 2.1. Introduction to suspended-core bers When the size of a waveguides core is signicantly larger than the wavelength of light, light is essentially conned within the core material, with only the tails of the guided mode protruding into the surrounding medium. This is often described in the literature as the evanescent eld, and sensors based on the interaction of this light with materials to be sensed are generally referred to as evanescent eld sensors. One way of facilitating access to the evanescent eld is to remove part of the cladding of a conventional coreclad ber to create a D-shaped ber [12]. However, the limited light available outside the ber core restricts the performance of sensors based on such bers. A more effective approach is to scale down the size of the core so that the guided light is no longer predominantly conned to the core, and Section 2.2 reviews this regime in detail. Conceptually, the simplest form of such a waveguide is a nanowire. Most glass nanowires reported in the literature have been produced via tapering bers with outer diameter > 100 lm to freestanding nanowires of 50900 nm [13]. However, such structures are fragile, which makes them difcult to handle, and fully exposed to the environment, which can lead to contamination and degradation. There are two approaches that can address these issues while retaining the capacity of the nanowire to act as a sensing platform: free-

standing nanowires can either be embedded within a porous substance (e.g. an aerogel [14]) or the nanowire can be suspended within a structure with larger outer dimensions [15]. The later approach can be realized via the direct drawing of optical bers with sub-wavelength core sizes (<1 lm) and practical outer diameters (>100 lm). One such ber structure is based on a high air lling fraction microstructured optical ber with a small core suspended via three thin struts, as shown in Fig. 1. While bers of this type have been studied extensively both for sensing and nonlinear applications, it has only been as a result of recent fabrication innovations that it has been possible to push the core sizes in such bers down to sub-wavelength scale dimensions [15]. For nanoscale core dimensions, the core acts as a suspended nanowire. The suspended nanowire in a suspended-core ber is supported within and protected by the solid outer cladding. Such structures offer the practical handling characteristics of an optical ber whilst retaining the optical characteristics of a nanowire. Using this approach it is possible to fabricate long lengths of bers with nanoscale core dimensions that can be used as the basis for robust sensing devices. The presence of small transverse features strain the capacity of established theoretical constructs to provide an accurate description of the optical properties of these bers. This section starts by presenting some recent advances in the understanding of bers with sub-wavelength features (Section 2.2), reviews the fabrication techniques used to such bers (Section 2.3), and nishes with an analysis of the loss of these bers (Section 2.4). 2.2. Light connement in waveguides with sub-wavelength scale cores theoretical considerations Consider a strand of glass with refractive index ng and diameter d, immersed in a material of refractive index nl. When d is larger than the wavelength of light k only the tails of the guided mode protrude into the surrounding medium. If a waveguides dimensions are reduced (i.e. d is decreased), at rst light becomes more tightly conned, until for some core diameter, dmin, (the value of which depends on the refractive indices), the mode is optimally conned. For core sizes d < dmin, light spreads out into the surrounding medium, and the structure starts to function as an optical nanowire [13]. This is a regime of particular interest for sensing applications, since such structures enable strong interactions between the guided light and any material in which the core is immersed. Note that evanescenteld terminology, while in widespread use, is perhaps misleading for these nanorail-like structures, in which most of the guided light is located outside of the solid material.

Fig. 1. Suspended-core lead silicate F2 optical ber fabricated at the University of Adelaide. Left: SEM of the whole ber cross-section. Right: SEM of the core region of the ber. The central triangular feature is the nanoscale ber core.

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One convenient measure of the mode connement is the effective mode area. A generalized denition of the effective mode area of a guided mode is:

Silica F2
0

R   e h ^dA z Aeff R 2 je h ^j dA z

1
Aeff (m2)

10

SF57 Bi

where e and h are electric and magnetic vector elds of the guided mode. Note that for core dimensions comparable to or less than dmin, the structure is single-moded, as can be seen in Figs. 8 and 9, where the entrance of higher order modes for larger core sizes is evident from the sharp features in the curves. Intuitively, the values of both dmin and the minimum Aeff decrease with increasing ng and decreasing k. It is important to note that this denition of Aeff, which was derived in [16], is a generalization of the standard denition based on the transverse eld [17] that takes into account the full vectorial nature of the guided mode eld. This is critical when considering optical bers with sub-wavelength scale cores; as shown in Ref. [16], when the core of a ber is sufciently small, some of the guided modes energy is polarized along the propagation (z-) direction, and the mode is no longer transverse. This has the effect of making the mode more tightly conned for structures with core sizes near dmin, since the z-polarized light is more tightly conned than the transverse polarized light. Fig. 2 shows Aeff as a function of d both for a rod of glass of index ng immersed in air (nl = 1.0, solid lines), and in water (nl = 1.33, dashed lines) for four different nanowire materials, ranging from silica glass to the relatively high index bismuth glass. Fig. 2 shows Aeff calculated using the conventional denition from [17], while Fig. 3 shows Aeff calculated using the denition given in Eq. (1). The rst point to note from these gures is the signicantly different values obtained using the general, vectorial model, particularly for values of d around and below dmin and for the materials with relatively high refractive indices. The validity of this generalized form for Aeff has been proven experimentally via measurements of the effective ber nonlinearity (c) [8]. Fig. 3 shows that for air-clad nanowires in the range 1.5 < ng < 2.0, 260 < dmin < 420 nm for a wavelength of 633 nm, with values of Aeff ranging from 0.06 lm2 to 0.2 lm2. For even smaller cores, light becomes increasingly located outside the core. The dashed lines in Figs. 2 and 3 show the light connement when the nanowire is immersed in water, which is a reasonable

10

= 632 nm Vectorial model

0.2

0.4

0.6

0.8

1.2

Core diameter (m)

Fig. 3. As for Fig. 2, but using a fully generalized vectorial denition of Aeff taken from Ref. [16].

approximation to the conditions that exist when chemicals or biomolecules are sensed in aqueous solutions. As might be expected, immersion has the greatest impact on the connement when materials with relatively low refractive index (such as silica glass) are used. Immersion shifts the value of dmin to slightly larger core diameters. The results presented to this point are for nanowire geometries. As discussed earlier, there are practical reasons to use suspendedcore bers as alternatives to nanowires, and for this reason, mode connement data for bers of the type shown in Fig. 1 is presented in Fig. 4. The results in Fig. 4 are for water-lled bers only. Note that in Fig. 4, the dashed lines represent results of the vectorial model and the solid lines are the scalar model. Observe via comparison of Figs. 3 and 4 that the mode connement is slightly weaker in the suspended-core ber, which is as expected since the supporting struts in the suspended-core ber slightly increase the effective refractive index of the cladding. Fig. 5 shows the modal power, PF, that is located within the holes of the suspended-core ber (expressed as a percentage). PF is dened as:

R S dA RH z PF S dA 1 z

Silica F2 SF57 Bi
0

Silica F2
10

Aeff (m2)

10

Bi

10

= 632 nm Standard Model

Aeff (m )

= 632 nm
0 0.2 0.4 0.6 0.8 1 1.2

Core diameter (m)

Fig. 2. Effective mode area (Aeff) for a circular nanowire as a function of core diameter d for four different glasses; silica (n = 1.45), F2 (n = 1.62), SF57 (n = 1.8) and bismuth (n = 2.09) for a wavelength of 632 nm using the standard denition of Aeff taken from Ref. [17]. Solid lines correspond to air-suspended nanowires, dashed lines to water-immersed nanowires.

10

Suspendedcore fiber waterfilled

0.2 0.4 0.6 0.8 1

Core diameter ( m)
Fig. 4. Vectorial effective mode area (Aeff) for water-lled suspended-core optical ber of the type shown in Fig. 1 as a function of core diameter for three of the glasses as Fig. 2. (Dashed lines: vectorial model, solid lines: standard model.)

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100

Silica
80

F2 Bi

PF (%)

60

= 632 nm Suspendedcore fiber

40

waterfilled

20

0.2

0.4

0.6

0.8

1.2

Core diameter ( m)
Fig. 5. Percentage of the modal power (PF) located within the holes of the waterlled suspended-core bers from Fig. 4 (vectorial model only).

where H refers to integration over the holes within the cross-section. Observe that for the case when the holes are lled with water, to get more than 50% of the guided mode outside the glass, the core needs to be <350 nm in diameter for F2 glass. Thus, to make use of this strong interaction regime, it is necessary to use bers with nanoscale core dimensions. Section 2.3 describes how such bers can be fabricated. As described above, the move to bers with sub-wavelength core dimensions is motivated by the need to enhance the proportion of the guided light located outside of the core material. Another interesting characteristic that emerges for bers with such small cores is the formation of highly localized high-intensity regions at the edge of the core. These regions have an impact on the performance of sensors based on these bers, increasing the efciency of both the excitation and the recapture of uorescence even for sensors in which uorophores are distributed throughout the uid volume in the holes [32]. This effect also has interesting implications for increasing the sensitivity of surface-based sensors, where it is possible to place the analyte in the most intense region of the optical eld. 2.3. Fabrication of suspended-core bers Suspended-core bers have been demonstrated in a range of materials including silica, lead silicate, tellurite and bismuth glass. Advances in the extrusion and drawing of soft glass optical bers has enabled the fabrication of optical bers with the smallest core diameters produced to date without tapering; cores as small 420 nm have been achieved in F2 lead silicate glass [15]. Soft glasses can be processed at lower temperatures than silica glass, and so it is possible to introduce virtually arbitrary crosssectional structures [18] via the extrusion of glass billets, which produces structured glass preforms in a single-step process. It is now possible to fabricate MOFs from extruded preforms with loss values equal to that of the bulk glass material (to within measurement errors), thus indicating that extrusion-related losses can be negligible [19]. To reach sub-wavelength core dimensions, the bers are made using a three-step process. Firstly, the structured preform and jacket tube were extruded from billets of glass. The outer diameter of these extruded items was in the range 1015 mm. To achieve bers with nanoscale core sizes and practical outer diameters, large ratio of outer to inner diameter and outer to core diameter are selected for the tube and structured preform, respectively. In

the second step, the preform is reduced in size to a cane of $1 mm outer diameter using a ber drawing tower. The cane is then inserted into the jacket tube. The outer diameter of the cane is selected to provide a close t to the inner diameter of the jacket tube. This assembly is then drawn down to form the nal ber. Careful adjustment of the drawing speed allowed accurate control of the outer diameter of the ber (within 1 lm in 110200 lm), and thus to a similar relative error in size of the core itself. From a single cane-in-tube assembly a few hundreds of meters of ber can be drawn. Fig. 6 shows examples of cross-sectional images of preform, cane and bers made using Schott F2 lead silicate glass (top row) and Asahi bismuth glass (bottom row). Dimensions of features in the bers were measured from cross-sectional scanning electron microscope (SEM) images. The core diameter, d, measured from SEM images of the ber cross-sections, is the diameter of the largest circle that can be inscribed in the core region. Since the area of this circle is smaller than the area of the triangular core region in the ber, it leads to an underestimate of the core area, and so we also dene the effective core diameter, deff to be the diameter of a circle whose area is equal to a triangle that ts wholly within the core (i.e. deff = 1.286 d). Comparison of the core size scaling of the mode area of suspended nanowires with a triangular core region (as for the bers presented here) with that of freestanding circular nanowires demonstrates that the use of the effective core diameter enables direct comparison of the optical properties of suspended-core bers with nanowires at a given core size [15]. The measured core diameters for the F2 and bismuth glass bers shown in Fig. 6 are 480 nm and 530 nm respectively. These core dimensions are somewhat above dmin for wavelengths in the visible and are below dmin for wavelengths in the near-IR (note that the location of dmin has been conrmed experimentally at 1550 nm for the bismuth ber via nonlinearity measurements [8]). Reference to Fig. 4 indicates the fraction of the light in water-lled holes is 26% for a 480 nm core F2 ber and 6% for a 530 nm core waterlled bismuth ber (@632 nm). Thus it is now possible to fabricate bers that offer substantial access to the guided eld for sensing. However, as described in more detail in Section 3, to assess the performance of any sensor based on these bers, it is necessary to characterize the ber loss. The loss in these suspended-core bers is reviewed in Section 2.4. 2.4. Loss in suspended-core bers One of the key reasons why optical bers are compelling platforms for sensing is as result of their capacity for low loss propagation; it is the long interaction length between the guided light and the substance to be sensed that gives this platform an advantage over non-guided light sensing congurations. Thus, while it is clear from the results presented in Section 2.1 that the light-matter overlap can be large in suspended-core bers, one must consider the impact of the choice of core size on the ber loss. A number of distinct loss mechanisms can come into play in this class of bers; most notably material absorption, loss resulting from fabrication-related imperfections, scattering loss due to surface roughness and connement loss. For larger (>2 lm) core suspended-core bers, the ber loss tends towards the material loss, indicating that fabrication, connement and scattering losses are negligible [19]. In the small-core ber regime under consideration here, the losses are signicantly higher. There are two key reasons why loss increases as one scales down a ber cross-section. The rst loss mechanism that can impact small-core MOFs is connement loss. For example, for the F2 glass suspended-core ber in Fig. 6, we observed pronounced connement loss at 1550 nm for core sizes d < 500 nm (as evidenced by strongly increasing loss at longer wavelengths), whereas for the higher

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Fig. 6. Cross sectional images of preform, cane and ber made using F2 glass (top row) and bismuth glass (bottom row). The measured core diameters for the F2 and bismuth ber are 480 nm and 530 nm, respectively.

standing nanowires (all other curves) and from the literature [21 23]. It is clear from this gure that both the magnitude and core size scaling of the loss of the air-suspended nanowire cores agrees well with that of freestanding nanowires. This is strong indirect evidence that the loss in supported nanowires is dominated by scattering loss due to surface roughness, as indeed is the case for nanowires of similar dimensions. Unlike connement loss, there is no straightforward way of mitigating this loss mechanism, and thus it is thought to be the ultimate loss limitation of these small-core structures. We have shown here that there is a clear trade-off between light-matter overlap and interaction length. In other words, there is limited point in moving to ever-smaller core dimensions given that the loss increases dramatically in this regime. The optimal trade-off (and thus core size selection) depends on the sensing architecture, and some examples are explored in more detail in Section 3.

3. Fluorescence sensing architectures 3.1. Introduction to sensing approaches based on suspended-core bers Suspended-core bers of the type shown in Fig. 1 can be transformed into gas and liquid sensing architectures for chemicals and biomolecules in numerous ways, and these architectures are reviewed here. These bers are an attractive platform for liquid sensing because they can enable strong light-matter interactions, long interaction lengths and the use of small sample volumes. Note that while suspended-core ber designs are not unique amongst microstructured bers in providing these properties; they are the simplest ber geometry that can offer these characteristics. More specically, these designs are optimal in terms of offering both nanoscale core dimensions, allowing for large light-matter overlap, and relatively large air holes, allowing for easier lling with gases or liquids. The most straightforward sensing architecture that can be adapted to the suspended-core ber architecture makes use of absorption spectroscopy. For example gases such as methane and acetylene are detected by monitoring absorption features in the mid-IR spectrum [24], and commercial devices are available that can detect chemicals of interest and particulates using UVVis light [25]. To create a suspended-core absorption sensor, the holes within the cross-section of the ber shown in Fig. 1 need to be lled with a gas or a liquid to be sensed, and this approach has been used

Fig. 7. Compilation of measured propagation losses at 633 nm and 1550 nm for a range of nanowires (freestanding and suspended) of different cores size and made using different glasses as reported in the literature.

index bismuth ber in Fig. 6 this was not observed. It is possible to substantially reduce the connement loss in the F2 ber by lengthening the struts within the suspended core design. Thus connement loss can be essentially eliminated via appropriate ber design. Note that when the bers are lled with uids, connement losses increase, and thus care needs to be taken to design the bers in terms of the optical characteristics of the lled ber. The second loss mechanism that impacts small-core MOFs is scattering associated with surface roughness on the core interface [20]. Fig. 7 is a compilation of loss values for different nanowire materials for both suspended nanowires (red1 curves) and free1 For interpretation of color in Figs. 25, 710 and 19 the reader is referred to the web version of this article.

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with a range of index-guiding and photonic bandgap guiding MOFs [2628]. The key considerations for the development of a MOF-based absorption sensor are as follows: Does the ber guide light over the spectral region of interest for the species to be sensed? How difcult is it to ll the holes with the sample? What is the tradeoff between light absorption and interaction length? Can molecules of interest be selectively detected in complex samples? One advantage of MOF-based absorption sensors, which has not to date been exploited, is the use of mid-IR transmitting glasses for the fabrication of suspended-core bers. A number of soft glass materials, such as uoride, chalcogenide and tellurite glasses, transmit light within the mid-IR spectral region. Recently, uoride glass MOFs that can transmit light out to 5 lm wavelengths have been reported [29]. It can be anticipated that the development of suspended-core bers using such materials will allow advances in mid-IR absorption sensing, particularly for gases. One important consideration for any lled MOF-based sensors is the rate at which the ber can be lled. For gas-lled bers the holes are lled via diffusion [30] and liquid-lled bers are lled via capillary forces as governed by NavierStokes equations [28], although lling rates are generally approximated with simpler capillary theory [31]. One can improve the lling rates by increasing the gas temperature or by applying an external pressure [28]. As a rule of thumb, lling MOFs with gases is prohibitively time-consuming, even for the case of suspended-core bers, which offer relatively large cladding holes, and in general to make such congurations more practical alternative geometries with side-access ports are desirable (see Section 3.5). In contrast, the pressure-assisted liquid lling of MOFs is practical, and it typically takes only a few minutes to ll the short (1020 cm) lengths of suspended-core bers that are typically used for uorescent sensor congurations. Fluorescence-based sensing architectures have been explored extensively in suspended-core bers [3234]. Consider a suspended-core ber dipped into a liquid that contains a molecule of interest labeled with a uorescent marker (such as a quantum dot or an organic uorophore). The uid begins to ll the holes of the ber. If light is launched into the guided mode(s) of the ber at a wavelength that is absorbed by the uorophore, a proportion of the longer wavelength emission from the uorophore is captured by the ber, and can be detected from either end of the ber. The ber core serves both as a means of efciently exciting and collecting the uorescence, and the strong interaction of the guided light with the liquid in the holes allows this approach to achieve high sensitivity and use small sample volumes. Section 3.2 provides an overview of work that has been done to develop tools for analyzing and optimizing the performance of these uorescence sensors. Section 3.3 describes the simplest practical form for these uorescence-based sensors: that of a dip sensor. 3.2. Fluorescent sensor design A theoretical model based on an analysis of the ber modes has been developed to explore the operation of these uorescencebased liquid sensors [3234]. This model, which has been experimentally validated [34], can be used to predict and optimize the performance of these sensors, and enables the selection of the most suitable suspended-core ber (or indeed any other MOF design) for a given sensing requirement. While it has been recognized for some time that it is important to increase the fraction of the modal power located in the holes [2] (to enhance the uorescence excitation), this model reveals that it is equally critical to understand the efciency with which the uorescence is captured by the guided mode(s) of the ber. The following expressions for the uorescence capture are based on the derivations developed initially in Ref. [32] and gener-

alized in Ref. [34] to include the contribution of higher order modes and to incorporate loss mechanisms encountered in practice in these small-core bers. We assume that the uorescent sources are contained within holes within the ber, and that they have random phase and orientation. Taking into account ber loss and Beers law absorption along the length of the ber, the fraction of uorescence (FCF) that is excited by excitation mode j, captured into all guided modes m of the ber at the uorescence wavelength, and propagates to the output end of a ber can be expressed as:

FCFj

H c L nk2 X NOIjm cj e m cm cj L F e 1 H2 16pnF m Aeff ;m cm cj

NOIjm

nH F

e0 l0

1=2 "R

A1

#"R # jsm ~ rjdA j~m j2 sj ~ e rdA H R R s ~ rdA jsm ~ 2 dA rj H j A

1

Aeff ;m

R 2   rdA  A1 sm ~  R 2 r js ~ j dA A1 m

where A1 is dened to be the innite transverse cross-section, L is the ber length, F is the uorescence wavelength, H refers to integration over the sensing region (ber hole(s)), sj(r) is the z-component of the Poynting vector of the jth mode, ej(r) is the electric eld of the jth mode, and c is the attenuation coefcient [35] A similar expression can be found for uorescence that propagates to the launch end of the ber [33]. Unsurprisingly, this model predicts that capture of the uorescence photons increasing with increasing refractive index difference between the core and cladding. More intriguingly, it was found that the existence of localized high-intensity electric and magnetic eld layers within the fundamental mode at the boundary interface of small-core bers leads to a substantial increase in uorescence capture when high index glasses are used [32], with these bers offering an order of magnitude improvement in the uorescence capture than lower-index ber variants. Eqs. (3)(5) can be used to identify the suspended-core bers that are best suited for low-concentration uorescence-based sensing [34]. Fig. 8 shows the calculated uorescence capture fraction (FCF) as a function of the core diameter calculated using this model for the case of a glass nanowire immersed in water. This is approximately equivalent to a suspended-core ber lled with an aqueous analyte. Several glass types with differing refractive indices (silica n % 1.46, lead silicate (F2) n % 1.62, bismuth n % 2.09) were considered for the nanowire material, with an excitation wavelength of 532 nm and a uorescence wavelength of

Fig. 8. Calculated uorescence capture into the fundamental mode only (thin lines) and into all guided modes (thick lines) for three different glasses where the nanowire is immersed in Rhodamine B dissolved in water. Results taken from Ref. [34]. The green curves correspond to silica glass, the red curves to F2 glass, and the black to bismuth glass.

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590 nm (Rhodamine B dissolved in water). The loss of the ber was taken to be zero and the ber length to be innite in this calculation. In this way, the calculated FCF represents the fundamental limit on the uorescence capture possible for the sensor design. The fundamental mode alone has been used to construct the excitation eld. All guided modes of the ber are excited to some degree by the uorescence, and the results for the capture fraction summed across all of these modes are shown in Fig. 8. As mentioned above, it is clear from this graph that the uorescence capture is greatest for bers with the largest core-cladding refractive index contrast, regardless of the core diameter. Additionally, we observe that uorescence capture into the fundamental mode only represents a signicant portion of the overall capture for very small core diameter bers ((1 lm). For larger cores, the uorescence capture is achieved mostly through the higher order modes. In fact, we see that the contribution of the higher order modes is such that the uorescence capture efciency becomes essentially insensitive to core diameter as the core diameter (and thus the number of modes), is increased. The sharp peaks in the curves of Fig. 8 correspond to capture into higher order modes near cut-off. When connement loss is considered, as is done below, these peaks become less sharp. While the results of Fig. 8 show that the uorescence capture efciency is relatively insensitive to the core diameter, they do not consider the effect of absorption of the pump light along the ber length, which depends on the fraction of power outside the core (PF) as well as the chemicals absorption coefcient. The curves in Fig. 9 correspond to more sophisticated theoretical predictions that also include the effect of uorophore absorption, connement loss, and core size dependent surface roughness loss. The data points in Fig. 9 correspond to experimentally measured uorescence capture results. For details of the experimental measurement techniques, see Ref. [34]. Note that no free parameters have been used. The experiments compare well quantitatively with theory, particularly for low-concentration samples. For higher concentration samples (P25 lM), the measured results are lower than expected, and reasons for this may include concentration quenching [36], or stronger than estimated reabsorption. The experimental results conrm several important points. Firstly, for high concentration samples the dependence on core diameter is quite small. This is due to near-complete pump absorption even at large core diameters. In contrast, stronger signals are obtained from smaller cores when low-concentration samples are

used, with up to an order of magnitude difference observed between 600 nm and 2 lm core diameter nanowires. To conclude, evanescently excited uorescence is most efciently captured into bers made from high refractive index materials due to their relatively high numerical aperture. There is very little dependence on core diameter when considering only the uorescence capture, due to the role of higher order modes. However, when one also considers the Beers law absorption of the excitation light, small-core bers can provide a stronger uorescence signal for low-concentration sensing. The absorption characteristics of suspended-core bers (Section 2.4) lead to the recognition that there is a minimum practical core diameter ber for uorescence sensing. For example, a 1 m long F2 nanowire would not be useful if the core diameter is less than %400 nm. Such results serve as guidelines for optimal sensor designs. 3.3. Dip sensing As mentioned in Section 3.1, the excited uorescence can be collected from either end of the ber. When a suspended-core ber is dipped into a liquid, the liquid is drawn up into the holes within the ber cross-section. If one collects the uorescence light traveling in the counter-propagating direction to the pump light, then it becomes possible to leave the distal end of the ber immersed in the liquid. In this way, it is possible to construct a dip sensing architecture. There are a number of advantages of this approach. Firstly, it allows for rapid sensing; the ber can be dipped into a liquid, and as soon as the liquid begins to enter the ber, uorescent photons begin to travel back towards the launch end. Once the interaction length between the liquid and the guided light is sufciently large that a signal can be detected, a measurement can be made (this occurs instantaneously for sufciently high uorophore concentrations). This approach also avoids the need for optical components at both ends of the ber. It also means that the performance of the sensor is only weakly dependent on the ber length used in the measurement [33], which differs from the case where the forward-propagating uorescence is captured, where the propagation loss of the ber leads to the existence of an optimal sensing ber length. Lastly, it allows the use of truly tiny sample volumes. For example, when a 10 cm length of the ber shown Fig. 1 is lled, the total sample volume enclosed within the ber cross-section is approximately 4 nL. In the simplest realization of a suspended-core ber dip sensor, the ber is dipped into a solution in which the molecule to be sensed is already uorescently labeled. This may take the form of labeled biomolecules (for example in Ref. [37] quantum-dot labeled proteins were detected within suspended-core bers) or uorophores that change their uorescent response in the present of a particular chemical of interest (for example in Ref. [38] suspended-core bers were used to quantify the presence of hydrogen peroxide over the range 1 nM to 500 nM via changes in the uorescence of the commercially available Amplex Ultrared uorophore from Invitrogen). Such sensors, while useful for characterizing the performance and sensitivity of the suspended-core optical ber sensing platform, are in themselves of relatively limited practical use because they require the sample to be pre-mixed or pre-labelled. There are two ways to address this without destroying the capacity of the platform to deal with tiny sample volumes: either the sample mixing/labeling can be done via the use of microuidic technologies, or the internal surfaces of the bers can be functionalized to provide the specicity required to identify particular molecules of interest. In the rst case the ber simply serves as a platform for enabling the lightliquid interactions and the use of small sample volumes. In the second case, the functionalized ber serves as a hybrid

1 2

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Fig. 9. Predicted forward-traveling uorescence signal for 0.26 m long F2 nanowires (solid lines) and measured signal for equivalent suspended-core bers (data points). For these predictions, ber loss (including connement loss) has been included. The excitation wavelength was 532 nm and uorescence wavelength was 590 nm. Rhodamine B concentrations were 50 lM (black), 25 lM (red), 1 lM (green), 100nM (blue), and 10nM (orange). Vertical error bars refer to signal uctuation during measurement (%10 s). Horizontal error bars correspond to the SEM resolution. Results taken from Ref. [34].

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optical sensor and chemical/biological recognition element. This approach is described further in Section 3.6. 3.4. Dip sensing example: sensitive detection of quantum dots in solution To demonstrate the performance of these suspended-core optical bers, results are presented here for a particular example that has been selected to demonstrate the current state of the art in terms of sensitivity of detection of this sensing platform. Fig. 10 (Left) shows the experimental dip sensing conguration used. In this experiment, 532 nm light is launched into a 1.8 lm core suspended-core ber made from Schott F2HT lead silicate glass. An SEM of this ber is shown in Fig. 10 (Right). This core size was chosen based on the insight provided by the model described in Section 2.2. A 533 nm LP lter (OD4 @532 nm, 99% at 534) was used at normal incidence to lter out the pump light. F2HT glass was chosen because it exhibits approximately half the material uorescence when pumped at 532 nm of the Schott F2 glass that has been used for much of our previous fabrication work. The uorescence signal of the glass, which arises from impurities within the glass, itself serves as one of the limitations on the concentrations that can be detected with this sensing platform. The ratio of the uorescence of the uorophore to the glass uorescence is a useful measure of the quality of the sensor: when this ratio is large, it is possible to make lower concentration measurements. This ber was lled with QDOT 800 solutions from Invitrogen of varying concentrations in a decane solution. Quantum dots have been selected here because of their signicantly increased photostability compared with organic dyes, enabling longer scans and higher laser powers without being affected by photobleaching, their high (%4 106 M1 cm1) absorption at 532 nm and the fact that they offer a large separation between the excitation and uorescence wavelengths, which avoids the need for ltering of the output signal. Fluorescence is collected in the backwards direction using a iHR320 Monochromator. Fig. 11 shows the measured uorescence. The different curves correspond to solutions with different quantum dot concentrations with the lowest curve being a ber lled only with decane to obtain a background glass uorescence level. This is used in place of an unlled-ber as the uorescence recapture changes signicant due to the signicant change in index contrast for the lled ber (1.62:1.0>1.62:1.41), resulting in a reduction in glass uorescence once the ber has lled. Detection of quantum dot concentrations down to 10 pM concentration has been achieved here, the lowest detection limit reported to date for this class of sensor. Further improvements in the detection limit will be possible via any combination of the following: reduction in the ber losses, further reduction in the material uorescence, the use of higher index glass materials, and the surface attachment of the uorophores.

Fig. 11. Measured uorescence from a suspended-core dip sensor lled based on the conguration and ber shown in Fig. 10. Curves correspond to solutions with different quantum dot concentrations.

3.5. Exposed-core bers: rapid lling and distributed sensing While in principle long interaction lengths can be achieved using suspended-core bers of the type shown in Fig. 1, in practice such bers can only be lled from one of the distal ends, and thus bers cannot be used as the basis for real-time sensing systems. If the analyte changes during the measurement period, emptying and re-lling of the ber is required. In addition, it is not possible to perform distributed sensing with traditional MOFs due to the requirement to ll from the distal ends. These issues can be addressed by exposing the core of the ber. Exposed-core bers were rst proposed in 2003 by Hoo et al. [30] and since been demonstrated by the use of a fusion splicer to blow holes within an MOF [27], use of a focused ion beam [39] and femtosecond laser micromachining [40]. Tapering of MOFs can also provide access to the guided eld [41]. However, all of these methods generally result in short exposed regions. Long lengths of exposed-core polymer ber have been fabricated by drilling holes into the cladding of the preform prior to ber drawing [42]. An alternative approach is the fabrication of exposed suspended-core ber via extrusion, using extrusion as a means of producing the highly asymmetric structures required [43]. Fig. 12 shows SEMs of exposed-core bers fabricated in F2 lead silicate glass via this extrusion technique. Details of the fabrication process for these bers are outlined in Ref. [43]. The performance of this exposed-core ber for uorescence-based sensing has been evaluated by placing it in a bath lled with a uorophore, with uorescence measurements made in the forward direction. The

Fig. 10. Left: Dip sensor experimental sensing conguration. 532 nm light is launched into a ber lled with a QDOT 800 solution in decane from Invitrogen. Fluorescence is collected in the backwards direction using a iHR320 Monochromator. Right: SEM images of the suspended-core ber fabricated from Schott F2HT lead silicate glass used in this experiment.

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signal response time for the exposed-core ber was <1 s [43], signicantly faster than for the enclosed suspended-core ber, which requires uid to ll into the small holes. Distributed measurement is a commonly stated advantage of sensing with optical bers. For example, distributed temperature sensors have been developed that utilize the temperature dependence of Raman or Brillouin backscatter [44]. There have been few reports on distributed chemical sensing [4547], largely due to challenges in nding appropriate cladding materials and uorescent dyes, and the low percentage of evanescent eld that is typically available to interact with the analyte [48]. Despite these issues, there exists a real need for such a technology because of their potential advantages in applications such as corrosion sensing [49,50], which explicitly require the capacity of distributed measurement for spatially locating corroded areas. As demonstrated in Ref. [51], the exposed core of the ber in Fig. 12 allows distributed uorescence sensing to be performed along the ber length using time resolved measurements. The experimental setup for this measurement is shown in Fig. 13; light from a multi-mode ber-coupled 780 nm diode laser (2 ns pulses, 25 kHz repetition rate) was coupled into the ber using a microscope to maintain the alignment of the laser on the exposed core. Different locations along the ber were then immersed into a bath containing an infrared active dye (IR-125, Exciton) with a concentration of 50 lM in 50% DMSO (dimethyl sulfoxide) in water. The ber ends were sealed prior to immersion to prevent uid entering the holes. Fluorescence was coupled into the modes of the ber via evanescent eld interactions. The output signal was ltered to remove the excitation light using a long pass lter, detected using a time-gated photomultiplier tube in photon counting mode (Hamamatsu R928), and analyzed using a modied Sentor 101 distributed temperature sensor [14]. Fig. 14 shows the time at which uorescence signal is detected from immersed portion of the ber. The peak location in Fig. 14 varies linearly with uorophore position, as expected. The longest piece of ber used in these measurements (2.5 m), was close to the range limit in this experiment due to the high loss of this ber: for a 0.5 m ber length there were %106 counts, while at 2.5 m the counts were reduced to %40. In these experiments, the ber loss is %11 dB/m, possibly due to the formation of surface cracks on the ber surface due to moisture. The spatial resolution was %0.5 m, primarily dictated by the laser pulse duration (2 ns), electronic sampling time (2 ns), and the length of ber immersed in the uorescent solution (3040 cm). This is the rst demonstration of uorescence-based distributed sensing using microstructured optical bers. Future improvements in the ber loss will allow the range to be extended to more practical lengths. 3.6. Adding specicity an introduction Section 3.3 described how suspended-core bers can be used as the basis for sensitive dip sensors that are capable of sensing within small uid volumes. Section 3.5 described how, by making the ber core accessible to the external environment, this platform

Fig. 13. Experimental setup for performing distributed uorescence measurements using the exposed-core ber from Fig. 12.

Fig. 14. Peak positions of reected pulses when the exposed-core ber is immersed in uids at various locations along its length. In the line of best t, T = signal time and L = position along ber.

can be extended to allow real-time measurements and distributed measurements. However, in both cases, these sensing architectures are only capable of measuring the uorescence of species that happen to be in solution. This is reasonable approach if, say, one is seeking to sense a molecule that causes a uorophore to undergo a well-characterized change in its uorescence in response to the molecules concentration, provided that one is prepared to mix the sample with the uorophore prior to loading the ber. Indeed, this is the approach that was used in Ref. [38] to quantify the concentration of H2O2 in solution using these suspended-core bers.

Fig. 12. Exposed-core bers fabricated from a WW preform with machined slot and a wedge-shaped jacket tube. The image sizes are (a) 170 lm, (b) 40 lm, (c) 200 lm, (d) 40 lm.

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However, the approach of measuring uorescence in solution is not always suitable for identifying (and quantifying) specic molecules. Here we describe advances in functionalizing the internal ber surfaces to create suspended-core bers for both chemical (Section 3.7) and biological (Section 3.8) sensing. For both classes of sensors, it is typically necessary to start by adding a thin chemical layer [52] to the internal glass-air surfaces, which serves as a base layer for covalently attaching indicator molecules (in the case of chemical sensing) or antibodies (in the case of biological sensing), and three distinct approaches for depositing coatings on the internal surfaces of the holes of a ber are described below. One approach is based on coating the internal surfaces with silane monolayers [53], and this has been used to coat soft glass suspended-core bers [54] and silica photonic bandgap bers [55]. The silanes bind covalently to surface hydroxyl groups via a condensation reaction. An alternative is to use polyelectrolyte (PE)based coating techniques [56,57]. The polyelectrolyte attaches to the glass surface using electrostatic forces. For example, poly(allylamine hydrochloride (PAH) is a strongly electropositive polymer that can bind to the weakly electronegative glass surface. Using silanes or polyelectrolytes with functional groups such as thiols or amines allows covalent attachment of further molecules of interest (such as antibodies or indicator uorophores) to silane or polyelectrolyte layers using cross-linker molecules or carboxylamine coupling reactions. For the example given in Section 3.7, we used PAH with a functional amine group to bind a uorophore molecule with a carboxylic functional group to the internal glass surface of a suspended-core ber. The internal surfaces of silica MOFs have also been coated with strands of DNA [26]. This approach uses poly-Llysine to immobilize negatively charged molecules such as DNA to a solid support. Poly-L-lysine has positively charged aminogroups that can bind to the negatively charged silica surface via ionic binding. The advantage of the second and third methods described above is that because the layer is attached to the glass via a physical (not chemical) means, it can be applied to different surfaces, including different glass surfaces. In all cases, these coatings are deposited by owing solutions through the voids in the suspended-core ber under controlled conditions. Once these coatings are deposited on the glass, it is then possible to add the desired chemical or bio-functionality by subsequently coating the surfaces with solutions containing chosen indicator compounds or antibodies, respectively. The best way of selecting the highest performing surface functionalization technique for a given sensing platform is assess the impact of this choice on both the optical loss of the ber and the binding density of molecules (indicator molecules or antibodies) that it enables. It is desirable to limit any additional optical losses in these sensing platforms because this diminishes the sensor performance, reducing the achievable light-matter interactions, and thus increasing the detection limit. It is also important to try to achieve the highest possible binding efciency to the surface to increase the interaction with the guided light and improve the response time of the device. Another important factor to consider is the conditions in which the sensor is to be used (for example, we have found that PE layers wash off in acid conditions). Ref. [57] describes a comparison of the performance of silane and PE-based coatings on the commonly used F2 soft glass using a strong, specic and well-characterized antibodyantigen interaction between biotin and streptavidin. This work demonstrates that the PE-based immobilization technique can represent a good alternative to silane-based processes. Firstly, for the conditions used in this work, the optical losses induced by the PE functional coating were found to be 25% lower than the silane counterpart. This has an impact on the sensitivity of the biosensor and enables a comparable sensitivity improvement. Secondly, the number of binding sites provided by the PE coating was found to be about 30% higher

relative to the silane coating. Note that PE coatings relies on surface charges rather than the covalent bonding of specic chemical groups (i.e. it is not dependent on the glass chemistry). 3.7. Chemical sensing example, an aluminum dip sensor In this section, the power of the surface-functionalized suspended-core ber platform to detect chemicals of interest is demonstrated. This is done by reviewing some recent work on the development of a dip sensor capable of detecting aluminum ions in solution without the requirement for pre-mixing of samples with uorescent dye solutions. This work is reported in more detail in Ref. [58], and this work represents the rst report of a surfacefunctionalized MOF-based chemical sensor. This sensor is of practical interest for applications such the monitoring of water [59,60] and food [61] quality, and for monitoring the corrosion of aluminum alloys [49,6264]. This sensor makes use of the polyelectrolyte-based surface functionalization strategy for a derivative of lumogallion, a compound that has a high sensitivity to aluminum (III) ions [60,63]. In these experiments the ber was rst internally coated with the polyelectrolyte PAH (described in Section 3.6) to allow a compound with a carboxylic functional group to be attached using a standard carboxylamine coupling reaction. Observe from Fig. 15 that the original lumogallion compound (L1), as reported in the literature, does not posses a functional group that is suitable to allow it to be coupled to a PAH layer. Therefore a derivative of lumogallion (L2) was synthesized inhouse with the aim of producing a compound with similar aluminum ion complexing abilities to lumogallion, but with a carboxylic acid functional group that can, in the presence of suitable coupling reagents, allow it to couple to PAH, and thus to bind to the functionalized glass surface, as shown in Fig. 16. Before testing the attachment of L2 to glass surfaces, its uorescence properties were compared to the original compound L1. We nd that L2s uorescence is lower than that of the original compound L1. However, this occurs for both complexed and uncomplexed forms of the compound, and thus is not necessarily disadvantageous because, as demonstrated below, competition with the uncomplexed lumogallion uorescence is generally the limiting factor when trying to detect low-concentrations of aluminum ion. Thus, in Fig. 17, the data is normalized relative to the 0 lM aluminum ion sample, demonstrating that there is very little difference in aluminum sensing performance between the two compounds. Most importantly, Fig. 17 shows that the lumogallion derivative L2 emits uorescence that increases with increasing aluminum concentration, making it suitable for this sensing application. To prove that the lumogallion derivative could be attached to a glass surface, both glass slides and suspended-core bers were tested. For both the glass slides and bers, two coating layers were applied; a single electropositive polyelectrolyte layer followed by a lumogallion layer. Experimental details are given in Ref. [58]. To measure the uorescence response of the coated slides to the presence of aluminum ions a uorescence imager was used (Typhoon Variable Mode Imager). This demonstrated a strong correlation be-

Fig. 15. Original lumogallion compound and the synthesized derivative of lumogallion used for surface functionalization.

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Fig. 16. PAH is an electropositive polyelectrolyte that can electrostatically bind to glass surfaces. The lumogallion derivative then couples to the PAH layer.

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After coating with PAH and then the L2 lumogallion, spectra were recorded just before (black curves) and 10 min after (orange curves) lling with the aluminum ion solution. No change in the background uorescence was observed with lling with the aluminum ion solution for concentrations of 3 mM or less. Results for concentrations of 10 mM and 30 mM are shown in Fig. 19. For the 10 mM samples there is a small increase in the uorescence signal after lling with the aluminum ion solution, and a large increase for the 30 mM sample. Note that these measurements were done in two pieces of ber (left and right columns in Fig. 19 correspond to measurements from each piece) and consistent results were achieved. These results demonstrate that the suspended-core ber can be used for aluminum sensing using the PAH-lumogallion coating method. However, the concentrations that could be detected in this early proof of concept experiment are two orders of magnitude smaller than that measured using the glass slide arrangement. This is due to the large amount of background uorescence occurring due to the presence uncomplexed lumogallion. This background uorescence was only present after the coating procedure, that is, it is not observed for uncoated bers and thus is not due to background uorescence from the glass. This implies that the surface density of attached lumogallion is actually too high to measure lower concentrations of aluminum. This work is a signicant rst step towards important applications such as water quality monitoring and corrosion sensing. 3.8. Specic biosensors based on suspended-core bers When one is seeking to specically detect a biomolecule of interest, whether that is a protein or a virus, it is necessary to employ biological recognition strategies such as the specic interaction between an antibody and antigen pair. This approach underpins widely used and highly sensitive commercial biosensing technologies such as Enzyme Linked Immunosorbent Assay (ELISA) technology [65], and can be adapted for use with a suspended-core ber geometry by immobilizing antibodies on the ber surface [66]. In other words, in order to introduce selectivity to a MOFbased biosensor, it is necessary to immobilize antibodies on the glass surfaces within the ber cross-section, most critically the interface with the ber core, where the efciency of uorescence excitation (and capture) is greatest. One advantage of using polymers as the host material for MOF sensors is that the surface can be chemically modied to allow biomolecules to be attached directly [67]. However, glass bers offer a number of advantages including the potential for lower loss and larger transmission windows. To make glass-based bers biologically active, a layer must rst be deposited on the bers internal glass surfaces that is capable of immobilizing/binding the antibodies, and this can be done using any of the techniques outlined in Section 3.6. Note that the PE-based methods are particularly well suited for biosensing due to the fact that biological samples tend to be close to pH neutral, and thus the coatings are at little risk of being washed away. Once a layer of antibodies has been immobilized on the glass surfaces, it is necessary to coat the ber with a solution containing a blocking agent; that is a species that will bind to the coating to prevent the unspecic binding of the antigen to the surface, thus, in principal, only allowing it to bind, specically, to the matching antibody. The efciency of this blocking step is critical, because without it, un-matched antigens can bind to the surfaces. (Note that in the rst demonstration of a suspended-core ber protein sensor [66], this blocking step was omitted.) Following the blocking step, the ber is coated with the solution containing the antigen (i.e. the sample is loaded into the ber), and specic binding between the antigen and the antibodies that are immobilized in

Ratio of fluorescence counts

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Fig. 17. Integration of the cuvette measurements of uorescence of the two forms of lumgallium (L1 = original, L2 = derivative) where the dark noise has been removed and the results divided by the 0 lM aluminum ion measurement.

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tween aluminum ion concentration and uorescence intensity for cases where the slide is immersed in the L2 compound after immersion in the PAH, whereas the controls slides show negligible response. This demonstrates that (a) the L2 compound is successfully attaching to the glass surface and (b) that it retains its concentration-dependent uorescence response to aluminum ions. This coating process was modied for use in a suspended-core ber, in this case a F2 glass ber with a core of %1.9 lm and a hole diameter of 12 lm, as shown in Fig. 18 (Left). It was fabricated using the techniques described within Section 2.3, but using active pressurization during ber drawing in order to inate the holes and thus improve liquid lling speeds and reduce hole blockages (note the relatively larger hole dimensions given the core size for the ber shown in Fig. 18 (Left) compared with the ber in Fig. 1). To coat the bers internal surfaces, solutions are forced through the bers internal holes using positive pressure by sealing the bers into a metal chamber and feeding regulated nitrogen gas into the chamber. The bers were cleaved into 6 cm pieces, placed into the setup shown in Fig. 18 (Right) and lled with various concentrations of aluminum ion solutions for 10 min using capillary forces only.

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Fig. 18. Left: Suspended-core ber with pressure-inated air holes, used in the chemical sensing experiments described in Section 3.7. Right: Setup used to measure the uorescence from the ber when lled with an aluminum ion solution. MMF is a multi-mode ber; LP is a long pass lter. A 633 nm laser was used for alignment into the spectrometer and turned off prior to measurement. Fibers were lled with aluminum ion solutions by immersing the right hand side end of the ber and allowing them to ll via capillary forces.

Fig. 19. Fluorescence counts for a surface functionalized aluminum sensor based on a suspended-core F2 ber. Each plot corresponds to a different section of ber that was tested. Black curves were recorded prior to lling the bers with an aluminum ion solution and correspond to background uorescence of the coating materials. Orange (Grey in black & white copies) curves were recorded 10 min after lling the bers with either a 10 mM aluminum ion solution (upper plots) or a 30 mM aluminum ion solution (lower plots).

the coating layer can occur. If one is using a label-free sensing technique, such as surface plasmon resonance, which can detect the binding event via a measurement of the change in density that occurs at the surface when binding occurs, this is the stage at which the detection is made. However, for the uorescence-based (i.e. label-based) approach described within this paper based on suspended-core optical bers, it is necessary to coat the ber surfaces with a uorescently labeled antibody following the antigenantibody binding event. This labeled antibody will bind to

the now immobilized antigen, and, following a washing step that is required to ush away any unbound labeled antibodies, it is now possible to conrm the presence of the specic antigen via the excitation and collection of the uorescence of the labeled secondary antibodies. This is a MOF-based variant of the ELISA sandwich detection technique. Some of the parameters that need to be measured, and optimized, in such systems include: the ber loss, the surface density with which the antigens are bound, the efciency of the blocking

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agent, the orientation distribution of the bound antigens, the afnity of the antibodyantigen binding system and the kinetics of these binding events. While Ref. [66] contains the rst work on the use of suspendedcore bers for protein sensing, in the future, by bringing together the recent advances in ber fabrication, sensor architectures, and biological coating techniques used with these bers, as outlined in this paper, we can expect to see signicant advances in the use of suspended-core bers for biosensing. The foundations now exist for demonstrating truly specic, sensing, dip sensors for specic biomolecules in solution.

4. Conclusions The capacity to fabricate microstructured optical bers with wavelength-scale and even sub-wavelength core dimensions has opened up new opportunities for light-matter interactions, particularly in the eld of liquid-based biological and chemical sensing. This new class of bers has required an improved understanding of the propagation of light within such structures, and has led to the development of generalized theoretical and numerical models to describe such bers. These models highlight some new physical phenomena such as the non-transversality of guided modes, and the presence of high-intensity light layers on the core/cladding interface, both of which inuence the performance of sensors based on these ber geometries. One particular new class of microstructured ber with particular potential for applications in sensing is the suspended-core optical ber. One can think of these structures as suspended nanowires, in which, as in a nanowire, the guided light can be substantially guided outside the solid core material, but in which the robustness of an optical ber geometry is retained. The relative simplicity of this ber design, which enables suspended-cored bers to be made from a wide diversity of optical materials, and the fact that it allows the combination of both tiny cores, which allow the guided light to emerge from the solid core material, and large surrounding voids, which are relatively easy to ll with samples under test, make this a powerful basis for new sensing technologies. They also offer the potential for working with tiny (nLscale) uid volumes, something unrivalled by existing sensing technologies. A number of new sensing architectures based on these suspended-core bers. This includes convenient and practical dip sensors that make use of backwards-traveling uorescence to determine the concentration of the chemical or biomolecules being sensed. Real-time and spatially distributed chemical sensors have also been demonstrated based on an exposed-core variant of the suspended-core ber, and such structures offer great promise for structural health monitoring. There remain signicant unexplored opportunities for the continued development of new sensing architectures based on these suspended-core bers. For example, little has been done to date to use such bers for gas sensing, and the potential for mid-infrared transmission in some soft glass materials makes this an attractive area for future research and development. To build on the existing body of work on the use of suspendedcore bers for liquid sensing, further work is required to improve our understanding of the ultimate limits of this platform in terms of sensitivity and performance. This will drive forward the fabrication of new bers, and will guide choices of the glass host material, loss targets and ber dimensions. Signicant work is also required to characterize and improve the robustness and practical handing of these bers, and one obvious next step includes the development of fully-spliced all-ber systems, which removes the need for alignment-sensitive free space optical components.

By adding surface functionality to the air-glass interfaces within the ber cross-section, it is now possible to imbue these suspended-core bers with rich new sensing capabilities. A range of surface functionalization strategies has now been demonstrated, including the use of silanes to covalently tether uorophores to the internal ber surfaces to enable them to respond to chemicals of interest, or antibodies to enable the detection of specic biomolecules. To date, this work has advanced by adapting existing techniques from the eld of biotechnology to the ber platform. To advance this eld to the next stage, it is increasingly becoming necessary to advance our understanding of the interplay between the optical characteristics of the modied surfaces, and their chemical and biological function. For example, the internal (and external) surfaces of the bers are re-polished during the ber fabrication process. This is indeed a key part of the reason why they are able to support low loss optical guidance. It also means that some of the techniques that are routinely used to enhance binding to these surfaces such as plasma processing [68] are likely to have a negative impact on the bers optical properties. However, it can be difcult to characterize the characteristics of functionalized surfaces, and measurements of key quantities such as the binding density often have to be made via indirect means, such as Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) or via uorescent labeling techniques. Now that the capacity to make sensors based on surface functionalized bers has been demonstrated, there is enormous scope for adding novel functionality to the surfaces of these bers. This will require dedicated synthetic and surface chemistry research, and can be expected to yield a suite of new ber sensing technologies. Such work also raises some interesting questions such as: How does the attachment of a uorescent molecule to a surface chance its emission? Can we use the guided light to modify the properties of the surface, for example to change the wettability of the surface, or to liberate a bound molecule and thus regenerate a sensor? Such questions, and other, indicate that this is likely to be a rich and fruitful are of research going forward. Acknowledgments T.M. Monro acknowledges the support of an ARC Federation Fellowship, and the support of ARC Discovery, Linkage and LIEF grants. The authors acknowledge the support of DSTO for research within the Centre of Expertise in Photonics. The authors acknowledge R.C. Moore for ber fabrication, T.-C. Foo for work on surface functionalization and Y. Ruan for early work on the protein sensing. References
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