Sensors and Actuators B 147 (2010) 137144

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Fabrication of carbon blackpolymer composite sensors using a position-selective and thickness-controlled electrospray method
Yong Shin Kim
Department of Applied Chemistry, Hanyang University, Ansan 426-791, South Korea

a r t i c l e

i n f o

a b s t r a c t
A shadow-masked electrospray method was used to fabricate a high performance carbon blackpoly(vinyl pyrrolidone) (CBPVP) composite sensor on a position-selected area of a sensor substrate. This new approach, when compared to the common drop-casting method, was shown to be much advantageous for the preparation of an active layer with optimum average thickness and porous microstructure, which is important to obtain high sensitivity and fast detection times. The thickness obtained was proportional to the electrospray scan number, and the eld-assisted generation of small droplets led to the formation of rough, porous microstructures. The CB content-dependent variation in sensor resistance exhibited percolation behavior with an abrupt decrease in the specic middle region with increasing CB content. The most sensitive methanol detection was observed for sensors with slightly larger CB content rather than that of the most rapidly varying midpoint in a percolation curve, which was probably due to increased susceptibility to noise resulting from high porosity. Polymer concentration was also observed to have a signicant effect on sensing properties owing to a change in lm morphology: the optimum concentration was approximately 0.25%, at which the conditions were suitable for the formation of a porous, sensitive sensor with a reasonable deposition speed. 2010 Elsevier B.V. All rights reserved.

Article history: Received 10 October 2009 Received in revised form 7 February 2010 Accepted 1 March 2010 Available online 7 March 2010 Keywords: Electrospray Film deposition Carbon blackpolymer composite Gas sensor Electronic nose system

1. Introduction Chemoresistive carbon black (CB)polymer composite sensors have attracted much attention as detection elements in electronic nose systems due to their broad response to diverse volatile organic compounds (VOCs) [110]. The diverse response comes from choosing the constituent materials (insulating polymer, additive plasticizer, and conductive CB) and by regulating relative quantities among them. This response was known to be based on the volume-transducing mechanism: the swelling of a CBpolymer lm upon exposure to vapor analytes generally leads to the increase in sensor resistance due to the separation between CB particles [3,6]. The ability to produce diverse sensors with excellent detection capability generates a great deal of exibility in the design of sensor array chips for electronic nose systems. A commercial product based on the composite sensors (Cyranose 320, Smiths Detection) was shown to be capable of rapid identication and assessment in application elds including the medical diagnosis of various human disease states [1114], and foodstuff quality [1517]. To produce an electronic nose system comparable to the dense, microscopic olfaction receptors of mammals, it is necessary to pre-

Tel.: +82 31 400 5507; fax: +82 31 407 3863. E-mail address: yongshin@hanyang.ac.kr. 0925-4005/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.snb.2010.03.002

pare a reliable array chip that is small in size and capable of sensitive detection. The fabrication of such an array chip requires the positioning of multiple sensors in a specic area with a pair of detection electrodes. The formation method used for active lms has a great effect on the physical properties of the lm, including thickness uniformity and porosity, which are important for the fabrication of sensors with high sensitivity and fast detection times. Currently, CBpolymer sensors are prepared by casting a composite solution, however the resulting lms are relatively large and non-uniform in thickness, and research to improve the formation process of the composite lms has limited to studies of conventional spray methods [18,19] or the use of sensor substrates with micromachined well structures [20,21] to form the composite lm in a well-dened area. Therefore, much work still needed to develop a position-selective and thickness-controlled deposition method for the development of a biomimetic sensor array chip. In this work, a shadow-masked electrospray method was utilized to deposit CBpolymer composite lms in a predened area with an optimum thickness. Within our best knowledge, this method is applied to produce the composite lms for the rst time although it had been already utilized to prepare SnO2 lm [22] and polymer particles [23]. Recently, Tepper et al. reported an array chip based on aligned CBpolymer composite bers using an electrospinning method [24]. The same experimental setup used in electrospinning was utilized for the electrospray process. However, the electrospray used a relatively low electrical eld and

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polymer concentration such that it produced sphere-like droplets different from the ber geometry produced via electrospinning. The electric eld-assisted spray method can produce smaller droplets and can more easily control the direction of moving droplets than the conventional pressure-driven spray. These characteristics will be ideal for forming a highly uniform, nanostructure-controlled CBpolymer composite sensing layer. In addition, the use of a shadow mask makes it possible to form a patterned composite lm in a small dimension of up to 50 m. The electrospray method was used to fabricate CBpoly(vinyl pyrrolidone) (CBPVP) sensors as a model CBpolymer composite system. It was arbitrary to choose PVP as an insulating polymer among many possible candidates. The CBPVP sensors have been reported to have broad response to VOCs and some specic interactions to analytes containing COOH and OH functional groups [25]. These sensors were prepared to have different levels of CB content, PVP concentration, and lm thickness. Their sensing characteristics were evaluated in terms of response magnitude and detection time upon exposure to methanol and benzene analytes. These results demonstrated that electrospray is a superb method for the formation of a sensitive CBPVP sensing layer with optimum thickness and porous microstructure. Furthermore, the position and size of the composite lm could be easily controlled by means of a shadow metal mask positioned on the sensor substrate. 2. Experimental Polymer solutions were prepared by dissolving PVP (Mw 1,300,000, Aldrich) in chloroform, having a concentra= tion ranging from 0.1% to 2% (w/w). After completely dissolved, 520 wt% CB particles (Black Pearls 2000, Cabot) in CB/PVP composite were added into the solution, and dispersed homogenously by physical agitation through ultrasonication treatment. CBPVP composite lms were deposited using the electrospray apparatus shown in Fig. 1. The composite solution was lled in a plastic disposable syringe, and inserted into a metal needle at a ow rate of 5 ml/h by pushing the plunger of the syringe using a syringe pump (KDS 100, KD Scientic). A sensor substrate covered by a metal shadow mask was placed on an electrically grounded stainless-steel plate. It was translated along a horizontal direction in reciprocating motion at a speed of 50 cm/s in order to obtain lms of uniform thickness. A high voltage of 6 kV was applied to the metal needle with a needle-to-substrate distance of approximately 20 mm. Composite sensors were fabricated on both at

glass and micromachined Si substrates with a pair of comb-shaped Au electrodes separated by 300 m. The Si substrate was bulkmicromachined to have a microheater-embedded membrane well (2 mm 2 mm) as previously reported in detail [21]. A shadow mask with a rectangular hole (0.5 mm 1 mm) was used for the micromachined Si substrate, and was positioned approximately 0.50 mm (corresponding to the thickness of a Si wafer) apart from the deposition plane, namely the detection electrodes positioned on the bottom of the micromachined well. Additional CBPVP lms were also formed by casting the composite solution of 1.0 l on the glass substrate for a comparison study. As-deposited CBPVP lms were dried for 10 h at 70 C under vacuum (102 Torr). Film thickness was measured by using a mechanical proler (AlphaStep 500, KLA-Tencor). Scanning electron microscopy (SEM; Sirion, FEI) was used to observe surface microstructures of the composite lms. Vapor detection characteristics were evaluated using a sensor measurement system consisting of a vapor-generating bubbler, analyte-diluted delivery lines and a small detection chamber as previously reported [26]. Measurements were carried out by placing the sensors in the chamber with electrical feedthroughs, and by blowing 1000 ppm methanol or benzene analytes over it at a ow rate of 1000 ml/min. The analyte concentration was regulated by adjusting a relative ow ratio between bubbler-through sample and dilution ow rates. Dry air was used as a carrier gas. An initial sensor resistance was measured by a digital multimeter (34410A, Agilent). Chemoresistive responses were measured by using a voltage divider circuit having the reference resistor with an identical magnitude to the initial resistance. As-obtained analog signals were amplied to utilize the full input range of the digital interface card (NI, DAQ 6062E) connected to a personal computer. Data acquisition was performed by the user software programmed under LabVIEW (NI) environments with a typical sampling rate of 10 Hz. Time-proled resistance data were rst pre-smoothed with their neighboring points to suppress unwanted high frequency noise. Two types of sensor response, i.e., maximum response Smax and effective response Seff , were obtained from the measured resistance data. The Smax was dened as the maximum percentage change of sensor resistance R with respect to a stabilized initial value Ro , Smax = 100 (R Ro )/Ro = 100 R/Ro , while the Seff was dened as the relative ratio of Smax with respect to the level of background noise NSD , Seff = Smax /NSD . The Ro value was obtained by averaging the resistance data immediately before analyte injection for 10 s. The NSD corresponded to the standard deviation calculated from the same baseline data. These two responses were determined by averaging the values obtained from three successive measurements. 3. Results and discussion 3.1. Comparison of electrospray and drop-casting methods A CBPVP composite lm was deposited by electrospraying composite solution (0.5% PVP and 17 wt% CB) on a glass substrate covered by a metal shadow mask with 300 m diameter circle holes. Fig. 2A shows an optical image of a lm electrosprayed with a scan number of 50 times, and the cross sectional thickness prole measured by the proler along the horizontal dashed arrow. The image clearly shows that the composite lm had a well-dened shape and specic position due to the aid of the mask. The lm was 275 m in diameter at FWHM. It had an average thickness of 590 nm and an rms roughness of 130 nm, exhibiting a severely rough appearance. Fig. 2B shows the corresponding image and thickness prole of a composite lm formed by casting a 25 nl drop of the same solution. Even though the volume used was very small, the diameter was longer than 1.5 mm. Compared to the electrosprayed lm, the cast lm was more irregular in shape and had

Fig. 1. Schematic diagram of the experimental design for the position-selective electrospray method.

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Fig. 2. Optical images (upper) and thickness proles (lower), along the dashed arrow, of CBPVP lms deposited by (A) electrospray and (B) drop-casting methods on a at glass substrate. The horizontal scale bars correspond to 500 m.

increased variation in thickness and CB distribution. These results seem to have occurred due to the difference in solvent evaporation time for the formation of the composite lm. In the electrospray process, almost all of the solvent that was ejected from the needle was in small droplets, and evaporated before reaching the substrate. In the cast lm, the process took approximately ten seconds for evaporation to occur. Therefore, CB distribution and thickness uniformity in the drop-cast lm were strongly inuenced by solvent evaporation dynamics. The longer evaporation time provided a higher probability that the CB nanoparticles would agglomerate and move within the composite solution according to the interactions between the solution and substrate, which might induce bad dispersion and non-uniform thickness for the drop-cast sample. Homogeneous dispersion of CB particles within the composite lms is advantageous to fabricate a sensor with good performance characteristics [8]. Consequently, the electrospray method was shown to easily deposit a specically sized and positioned composite lm with uniform thickness and homogenous CB distribution on a substrate compared to the conventional drop-casting and spin-coating methods. Moreover, the electrospray method effectively controlled the moving direction of the composite droplets with the aid of an applied electrical eld rather than the spray method based on high pressure. Surface microstructures were observed by SEM at the center region of CBPVP lms deposited by both electrospray and dropcasting methods (Fig. 3). These images show that the electrospray method developed more highly porous nanostructures than the

drop-casting method. A rough, porous morphology is advantageous to achieve a highly sensitive and fast responding sensor due to the high surface-to-volume ratio and the existence of many pores which serve as the analyte molecule pathway to the inside of the sensing layer. Electrospray and drop-casting methods were also applied to deposit a CB composite lm on a pair of detection electrodes located in the bottom of a Si bulk-micromachined membrane well. Fig. 4A shows a cross-sectional diagram of the sensor substrate with a microheater-embedded membrane structure. Fig. 4B and C show plane-view optical-microscope images of CBPVP lms deposited by shadow-masked electrospray and drop-casting, respectively. The electrosprayed lm was approximately 20% larger in size than that of the mask due to the 0.5 mm separation between the mask and deposition plane. This demonstrates that the position and shape of a lm can be controlled with the aid of a shadow mask in the noncontact electrospray mode, despite considerable deviation from the mask-dened size. The noncontact deposition had an advantage in that it avoided breakdown of the fragile membrane. On the other hand, the image of the drop-cast lm displayed serious aggregation and inhomogeneous distribution of CB particles. Although it was possible to limit the deposition area within the hollow well, the thicknesses of the bottom and side walls were observed to differ greatly and were strongly dependent on the composite solutions used; as at times the lm predominantly formed on the side wall while in other cases a thick lm on the bottom was identied. These results show that the electrospray method can be

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Fig. 3. Typical SEM images observed at the center region of CBPVP lms deposited by (A) electrospray and (B) drop-casting methods.

successfully utilized to deposit a sensing layer with uniform thickness on a fragile membrane, which is impossible to attain using other conventional methods. 3.2. Dependence on scan number Fig. 5 shows variations in average thickness and relative roughness for CBPVP lms electrosprayed with different scan numbers. Relative roughness was dened as a percent ratio of rms roughness with respect to lm thickness. It exhibits a good linear relationship between thickness and a scan number, ultimately demonstrating the ability to control thickness in the electrospray method simply by using a specic scan number. Therefore, the shadowmasked electrospray method can provide an opportunity to form a thickness-controlled composite lm on a specic position. Thickness control is difcult to achieve in the casting process while complicated patterning processes are necessary in the spin-coating method. Relative roughness showed a tendency to decrease exponentially. The rms roughness was found to increase steadily with ascending scan number. However, since the thickness increased more promptly than rms roughness, relative roughness became smaller as a scan number increased. Thickness-dependent sensing characteristics were investigated for CBPVP composite sensors prepared with different scan numbers. Fig. 6A through 6D show the response curves, i.e., variations in sensor resistance as a function of elapsed detection time, for composite sensors deposited with increasing a scan number from 20 to 70 cycles upon exposure to 1000 ppm methanol vapor. Sensor measurements were performed twice sequentially by injecting methanol vapor into the chamber with a duration time of 120 s. The initial sensor resistance progressively decreased from 17.1 k to 3.31 k as the scan number increased, which was expected based

Fig. 4. (A) Cross-sectional schematic for a shadow-masked Si bulk-micromachined sensor substrate with a membrane well structure. Optical images of CBPVP lms deposited by (B) electrospray and (C) casting methods on the Si substrate.

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Fig. 5. Variations in thickness (circle symbol) and relative roughness (square symbol) as a function of a scan number for CBPVP lms electrosprayed with 17 wt% CB and 0.5% PVP composite solution.

Fig. 7. Scan number vs. maximum response (Smax , square symbol) and effective response (Seff , circle symbol) for CBPVP sensors shown in Fig. 6.

on the increase in thickness of electrically conductive materials. When the scan number was less than 10 cycles, the initial resistance was observed to have a value larger than 1 G , which implied there was a threshold thickness necessary to form an electrical conduction pathway through the composite lm due to highly porous nature. Judging from the measured thicknesses of samples after 10 and 20 cycles, the threshold thickness was expected to be between 90 nm and 200 nm. Response times for the 20-cycle sensor were approximately 30 s, which was more than two times faster than the 70-cycle sample with a thickness of 760 nm. Consequently, fabrication of CB composite sensors must be regulated for optimum lm thickness larger than the threshold value to achieve a fast and reliable sensor. Sensing capabilities of the composite sensors deposited with different scan numbers were quantitatively evaluated in terms of two types of response; Smax and Seff . Fig. 7 shows the variation curves of

Smax and Seff as a function of a scan number, corresponding to lm thickness. The Smax exhibited a gradual decrease as a scan number increased while the Seff had its maximum value at approximately 30 cycles. The maximum point in Seff resulted from the relationship of Seff = Smax /NSD and the observation that the 20-cycle sensor had a higher NSD value than those with higher scan numbers. Since a composite lm with a thickness slightly higher than the electrical conduction threshold had insufcient electrical pathways for connecting the two detection electrodes, its detection signal was easily susceptible to random noise and outside perturbation. In the case of thick lms with a thickness larger than three times the threshold thickness (50- and 70-cycle samples), the responses became worse since the relative resistance change induced by interactions between the composite lm and analyte decreased, which was due to the presence of too many stable electrical pathways at the initial state. Therefore, careful thickness control is necessary to achieve a good performance sensor. The optimized thickness in the electrosprayed CBPVP sensor system was expected to be twice the threshold thickness, even though a sensor with a thickness close to threshold gave the best performances in response time. Scan number-dependent response was also investigated upon exposure to benzene analyte to conrm that the optimized scan number obtained from methanol measurements was effective for other analytes (Table 1). The benzene results clearly show identical sensing characteristics to methanol detection as a function of a scan number, including a gradual decrease of Smax , a high NSD at 20 cycles, the highest Seff value at 30 cycles, and a steady increase in response times. 3.3. Dependence on CB content The effect of the amount of CB particles on sensing property was investigated for CBPVP sensors electrosprayed using composite solutions with CB contents ranging from 5 20 wt% with the optimized scan number of 30 cycles. Fig. 8 shows the variation curve of the initial sensor resistance (Ro ) as a function of CB content, which displayed a logarithmic decrease with increasing CB content. This
Table 1 Summary of benzene-sensing characteristics of CBPVP lms electrosprayed with different scan numbers. Electrospray scan number (cycles) 20 30 0.24 0.0006 252 50 0.19 0.0006 215 70 0.16 0.0016 129

Fig. 6. Time-proled response curves of CBPVP lms prepared with different electrospray scan numbers in Fig. 5: (A) 20, (B) 30, (C) 50, and (D) 70 cycles. Methanol vapors at 1000 ppm were used as the analyte.

Maximum response, Smax Background noise, NSD Effective response, Seff

0.32 0.0018 161

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Fig. 8. Dependence of initial resistance on CB content for CBPVP composite sensors fabricated by the electrospray method.

Fig. 10. Time-proled response curves of electrosprayed CBPVP composite sensors with different PVP concentration. The designated numbers correspond to the PVP percentage concentration. The bottom square pulses exhibit time proles of supplying methanol vapors at 1000 ppm.

conductive behavior was explained by the well-known percolation theory [3]. To achieve a highly sensitive composite sensor, CB content was known to locate in the region where there was an abrupt resistance change in the percolation curve. Judging from the percolation curve obtained, the sensitive CB content was expected to occur at approximately 15 wt%. Fig. 9 shows CB content-dependent variations of 30-cycle electrosprayed sensors in terms of Smax and Seff for 1000 ppm methanol exposure. The Smax exhibited a gradual decrease as CB content increased, which was similar to the scan number-dependent variation observed above. This steady Smax decrease implies that a sample with lower CB content has less conductive pathways via CB particles, and these electrical channels are more greatly modulated by the adsorbed methanol molecules. In addition, the lower CB content also leads to the higher NSD since the conductivity by the limited pathways becomes more comparable to random uctuations. The Seff dened by Smax /NSD had a maximum peak at 17.5 wt%, which was slightly larger than the value expected from the percolation curves. Similar experiments were performed for sensors prepared with a scan number of 50 cycles. In this case, resistance changed sharply at approximately 10 wt%, and the maximum Seff was observed at 12.5 wt%. Consequently, these results clearly demonstrate that the sensing characteristics of composite sensors are strongly dependent on CB content. Therefore, regulation of CB content must be one of the most important factors in achieving a highly sensitive sensor.

The decrease in threshold resistance for sensors produced with a high scan number is an expected outcome due to the increase in conductive layer thickness. In addition, the general phenomenon appears to be that the CB content with a maximum Seff is larger than what would be expected based on the percolation curve of electrosprayed sensors. This discrepancy may be attributed to the porous nature of the electrosprayed lm as observed by a proler. Since a porous layer has a limited number of conduction pathways relative to a compact lm formed by drop-casting or spin-coating, the electrosprayed lm is more susceptible to electrical noise such that the maximum Seff can be observed at a higher CB concentration in the abruptly resistance-varying region. 3.4. Dependence on PVP concentration The effect of PVP concentration on composite solution was also examined due to a strong dependence of droplet formation and condensation dynamics on solute concentration in the spray process. Fig. 10 shows time-proled response curves of 30-cycle electrosprayed sensors fabricated using composite solutions with the same CB content and varying PVP concentrations ranging from 0.1% to 2.0%. The detection responses and times obtained are summarized in Table 2. The Smax and Seff had the maximum values of 2.10 at 0.25% and 551 at 0.5%, respectively. The detection times were found to decrease as PVP concentration increased. On the whole, optimum sensing characteristics were observed at the PVP concentration of 0.25%. These results clearly demonstrate that detection characteristics are also dependent on PVP concentration. To clarify the effect of PVP concentration, the thickness and microstructures of formed composite lms were investigated using a mechanical proler and SEM. These properties are determined by the dynamics of droplet formation and CBPVP condensation. In
Table 2 Summary of methanol-sensing characteristics of CBPVP sensors fabricated by electrospraying composite solutions with different polymer concentrations. PVP Contents (%) 0.10 Maximum response, Smax Effective response, Seff Response time (s) Recovery time (s) 1.03 244 42 55 0.25 2.10 525 48 68 0.50 2.04 551 57 86 1.0 1.44 320 88 128 2.0 0.85 175 97 184

Fig. 9. Variation curves of maximum response (Smax , square) and effective response (Seff , circle) as a function of CB content for electrosprayed CBPVP sensors upon exposure to 1000 ppm methanol.

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an electrospray process, the number density and size of droplets are mainly dependent on the experimental parameters such as an applied voltage, viscosity and surface tension of a composite solution. The droplet formation characteristics will be almost identical for the composite solutions with the PVP concentrations of 0.12.0% since the ejection force induced by the applied voltage of 6 kV is much larger than those from the small variations in viscosity and surface tension. The resultant microstructures of CBPVP may be mainly determined by the solvent evaporation and solute condensation dynamics. As would be expected, thicker lms were formed from the more concentrated solutions, although thickness was not directly proportional to PVP concentration, and this thickness differential must be one factor that determines the sensing properties mentioned above. On the other hand, porosity of composite lms was observed to be strongly dependent on PVP concentration. Fig. 11 shows SEM images of the condensed phases formed by electrospraying a few drops of the composite solution with different PVP concentrations. The images show that the microstructures formed varied signicantly from particulates, to porous agglomerates, to a continuous layer as the PVP concentration increased. From these observations it is expected that the composite lm formed with lower PVP concentration has a more porous microstructure, i.e., a high surface-to-volume ratio. It can explain the high sensitivity of CBPVP composites electrosprayed by using a solution with the optimum concentration of 0.25%. Although a sensor from the lowest 0.1% PVP concentration may have comparable or better sensing performance than the optimized one, use of such a low concentration would be inappropriate due to the requirement for an increase in electrospray scan number to reach a sensitive thickness. Therefore, the optimum PVP concentration may be correlated with conditions resulting in the effective formation of a porous lm together with suitable thickness. 4. Conclusion We proposed and tested a new process method based upon an electrospray technique that was appropriate for the preparation of an array of CBpolymer sensors to be used in miniaturized electronic nose systems. The shadow-masked electrospray method was conrmed to deposit a composite sensor at a specic position with a decreased diameter size of approximately 100 m, which should be small enough to satisfy the requirements for a small electronic nose system. Moreover, the electrospray method easily produced small droplets from the nozzle due to the strong ejection force formed by the high electric eld, so that it provided many opportunities to regulate the characteristics of composite lm microstructures. Through the comparative study, we experimentally determined that the electrosprayed lm had more uniform thickness and higher roughness than those produced by dropcoating method. These physical properties resulted in a sensor that was highly sensitive in the detection of methanol. Experimental factors such as electrospray scan number, CB content, and polymer concentration were found to signicantly affect the sensing properties of formed sensors. For the CBPVP sensors fabricated here, the optimized conditions observed for an active sensing layer were electrosprayed with 30 scan numbers for a thickness of approximately 300 nm using a CBPVP solution with 0.25% PVP in chloroform and 17.5 wt% CB content with respect to the PVP matrix.
Fig. 11. SEM images of CBPVP composites formed by electrospraying a few drops of composite solutions with different PVP concentrations in chloroform: (A) 0.1%, (B) 0.25%, (C) 0.5%, and (D) 1.0%.

Acknowledgement This research was supported by the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2009-0090894).

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Biography
Yong Shin Kim received a PhD degree in chemistry from the Korea Advanced Institute of Science and Technology (KAIST) in 1997. After his degree, he worked as a Senior Research Member with the Electronics and Telecommunications Research Institute in the eld of developing at panel displays, i.e., thin-lm electroluminescent devices and miniaturized electronic nose systems. Since 2007, he has been with Hanyang University. Currently, his research activities are focused on the development of miniaturized, smart chemical sensor systems and novel nanomaterials for sensor applications.