Open Access Article
Sung Ho Kima,
Jieun Limab,
Seonjeong Leea,
Myung Hyun Kanga,
Wooseok Song
a,
Jongsun Lim
a,
Sunsuk Lee
a,
Eun Kyoung Kim
b,
Joung Kyu Park
*a and
Sung Myung
*a
aAdvanced Materials Division, Korea Research Institute of Chemical Technology, Daejeon 34114, Korea. E-mail: parkjk@krict.re.kr; msung@krict.re.kr
bDepartment of Chemical and Biomolecular Engineering, Yonsei University, Seoul 03722, Korea
First published on 6th July 2021
Herein, we reported a wearable photodetector based on hybrid nanocomposites, such as carbon materials and biocompatible semiconductor nanocrystals (NCs), exhibiting excellent photoresponsivity and superior durability. Currently, semiconductor nanocrystal quantum dots (QDs) containing heavy metals, such as lead or cadmium (in the form of lead sulfide (PbS) and cadmium sulfide (CdS)), are known to display excellent detection properties and are thus widely employed in the fabrication of photodetectors. However, the toxic properties of these heavy metals are well known. Hence, in spite of their enormous potential, the QDs based on these heavy metals are not generally preferred in biological or biomedical applications. These limitations, though, can be overcome by the judicious choice of alternate materials such as silver sulfide (Ag2S) NCs, which are biocompatible and exhibit multiple excitons in Ag2S QDs. The other chosen component is a carbon-based material, such as the multi-walled carbon nanotube (MWCNT), which is preferred primarily due to its strong and superior mechanical durability. In this study, a hybrid nanocomposite film was synthesized from Ag2S NCs and MWCNTs by a simple one-step fabrication process using ultrasonic irradiation. Additionally, this method did not involve any chemical functionalization or post-processing step. The size of Ag2S NCs in the hybrid film was controlled by the irradiation time and the power of the ultrasonic radiation. Further, appropriate composition ratio of the hybrid composite was optimized to balance the photo-response and mechanical durability of the photodetector. Thus, using this synthetic method, an excellent photoresponsivity property of the device was demonstrated for a near-infrared (NIR) light source with various light wavelengths. Furthermore, no visible change in photoresponsivity was observed for bending motions up to 105 cycles and for a range of angles (0–60°). This novel method provides an eco-friendly alternative to existing functional composites containing toxic heavy metals and is a promising approach for the development of wearable optoelectronic devices.
In this work, we demonstrate efficient NIR photodetectors with hybrid nanocomposite films based on Ag2S NPs and CNTs. Nanocomposites based on CNTs and Ag2S NPs (CNT–ANs) were successfully synthesized by a simple one-step solution process using ultrasonic irradiation. The sonochemical method is an effective technique for the synthesis of nanomaterials with unique shapes and properties. Moreover, this technique has a strong enough propagation pressure to create bubble formation and to hold an incomplete collapse in the solution.15 The optimized synthesis of CNT–ANs was determined by adjusting the Ag2S proportion in CNT–ANs, and the NIR detectors based on CNT–ANs were characterized against light exposure at different wavelengths and photo power densities.
Our NIR detector based on CNT–ANs exhibits an excellent photo-response of 278.22 A W−1 under light exposure (wavelength of 800 nm) with a power density of 0.15 mW cm−2, which is considerably higher than that of photodetectors based on CNT–PbS.16 In addition, this synthetic method based on CNT–ANs allowed us to improve the physical flexibility and sensitivity of the photodetector; moreover, these materials exhibit excellent properties. These synthesis methods and optoelectronic properties suggest a facile and an efficient approach for fabricating hybrid optoelectronic devices for various applications, including flexible devices and advanced wearable sensors. Furthermore, it could prove to be a viable replacement to previous devices based on heavy metal materials.
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1, 1
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5, 1
:
10, and 1
:
20) of CNT–ANs. As a result, CNT–ANs were successfully synthesized and dispersed in a highly volatile alcohol-based isopropyl alcohol solvent. Additionally, Ag2S NPs, when dispersed in various organic solvents, were observed to remain intact without precipitation even after three months (Fig. S1 in ESI†) because of the presence of DDT as a protective coat on the surface of NPs.17 The CNT–ANs were then spray-coated on to SiO2 or polydimethylsiloxane (PDMS) substrates for the fabrication of the CNT–ANs film. Subsequently, it was annealed in a vacuum oven to remove residual solvents present within (Fig. 1 (a-ii)). In the final step, a metallic source–drain electrode was formed by thermal evaporation on top of the CNT–ANs film, as shown in Fig. 1 (a-iii).
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1 to 1
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20. Ag2S NPs were found to have grown on the CNT surface, and the size of Ag2S NPs was observed to increase with a corresponding increase in the proportion of AgNO3 added. Thus, large Ag2S NPs were observed when using small capping ligands, such as DDT, at relatively high reaction temperatures. Also, transmission electron microscope (TEM) investigation confirmed that the particle size of Ag2S NPs is approximately 10 nm (Fig. S2 in ESI†), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) shows the existence of C, Ag and S elements in CNT–ANs (Fig. S3 in ESI†). In addition, it was observed that the density of excess Ag2S NPs increased on the CNT surfaces during the synthesis of NPs, resulting in high proportions of Ag2S NPs.18 However, cracks in the CNT–AN films by excess Ag2S NPs resulted in a decrease in the electrical conductivity between grains (Fig. S4 in ESI†).19 Additionally, Ag2S NPs in CNT–ANs have poor crystallinity when using a low-power sonication radiation. Hence, NPs were synthesized successfully under a sonication radiation of high power for over 120 min (Fig. S5 in ESI†).20 The structural characterization of the various synthesized CNT–ANs (Fig. 1(c)) was performed using X-ray diffraction (XRD). A number of Bragg diffraction peaks of α-phase Ag2S NPs were observed at 2θ values of 26.323°, 28.966°, 31.521°, 36.557°, 36.806°, 37.719°, 43.407°, and 45.426°, which could be successfully indexed as (012), (111), (−112), (−121), (121), (−103), (200), and (−131) diffraction planes (Ag2S, #JCPDF 00-014-0072), respectively.21,22 In the XRD pattern of CNTs, the observed peaks at 25.919, 42.959, and 53.29° were assigned to (002), (100), and (004) diffraction planes (CNTs, #JCPDF 00-058-1638), respectively. Moreover, the XRD peak intensity of CNT–ANs increased with an increase in NP precursors indicating that the crystallinity of Ag2S was improved. Further, the observed XRD pattern of CNT–ANs was quite similar to that of the Ag2S NPs, suggesting that the internal phase structure of Ag2S does not undergo any significant change when combined with CNT. In particular, no characteristic (002) diffraction peaks of CNTs were observed in the XRD pattern of the hybrid nanocomposite CNT–ANs. The primary reason for this trend is the presence of low amounts of CNTs as large amounts of Ag2S are present on the surface. Moreover, as the ratio of Ag2S increased, the full width at half maximum (FWHM) value of the (−112) peak decreased, indicating that the particle size increased gradually.23
The surface chemical composition analysis of different proportions of CNT–AN samples was investigated via X-ray photoelectron spectroscopy (XPS) (Fig. 2(a)). The Ag 3d core level spectrum for the Ag 3d5/2 and Ag 3d3/2 peaks showed a strong intensity and a set of symmetric peaks at 368.08 and 374.28 eV, respectively. There were no shoulder or satellite peaks observed between the Ag 3d peaks. Further, the intensity of the peak too was observed to increase with an increase in the concentration of Ag2S. In the S 2p core-level spectrum, the S 2p1/2 and S 2p3/2 peaks were observed at 162.58 and 161.48 eV, respectively.24 The intensity of the silver peak was observed to increase gradually with the respective atomic ratios ranging between 1
:
1.33 and 1
:
2 (Fig. S6 in ESI†). All the obtained XPS profiles were calibrated against the C 1s peak located at 284.48 eV. The peak at 284.7 eV was assigned to the sp2 hybridized carbon (C–C), and the peak at 285.5 eV was assigned to the C–S bonding peak according to sulfur. When the survey peak in CNT–ANs was measured with various proportions of Ag2S, the intensity of the carbon peak decreased gradually with a proportional increase in the amount of Ag2S. In addition, as the ratio of Ag2S in the CNT–ANs sample increased, the intensity of the C–S bonding peak too was observed to become stronger. To compare the characteristics of CNT–ANs, three different samples of thin films were prepared based on CNT–ANs, mixtures of DDT with CNTs, and CNTs using the same synthetic method (Fig. S7 in ESI†). When DDT was added to the CNT solution, sulfur peaks associated with the DDT solution were observed. In addition, the mixture of DDT and CNT exhibited a low intensity for C–O and COOH bonding and a high intensity for the C–S bonding. On the other hand, when AgNO3 was added to the CNT–DDT solution mixture, sulfur peaks related to Ag2S in the thin film were observed. Moreover, a higher intensity of C–S bonding in C 1s was obtained this time when compared to its intensity values in the CNT–DDT only mixture (i.e. the mixture without AgNO3). This indicates that sulfur is formed first on the CNTs and AgNO3 reacts sequentially to form Ag2S NPs. Fourier transform-infrared (FT-IR) spectroscopy was used to investigate the surface modification of CNTs by DDT and AgNO3.25 The results are shown in Fig. S8 in ESI.† For CNTs, the spectra exhibited almost no functional groups on the surface. However, after synthesis, the CNTs revealed the presence of various kinds of functional groups. The bands at 2917 and 2848 cm−1 correspond to the C–H stretching vibrations. This indicates that the Ag2S NPs are bound to CNTs by a variety of functional groups.
As shown in the Raman spectra of CNTs, Ag2S NPs, and CNT–ANs (Fig. 2(b)-(i and ii)), the D-band, G-band, and D′-band peaks were measured according to the radial breathing mode (RBM) of Ag2S.26 In this case, the Raman spectra were recorded at an excitation wavelength of 514 nm. As the peaks at 1437 cm−1 arise from the vibrations of silver metal and sulfur oxide compounds, which are formed due to the photo-induced decomposition of Ag2S in air under the exposure of high laser excitation power (Fig. S9 in ESI†), the measurement was performed at a relatively low power (power < 0.86 mW) of the laser radiation.27 The RBM peak in the Raman spectrum originated from the phonon vibration mode of Ag–S bonding in Ag2S NPs. Broad peaks at 250 cm−1 were observed for Ag2S NPs, but not for CNTs. It is worth noting that Ag2S NPs were well formed on the CNT surface. However, in the case of the 1
:
1 (CNT
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Ag2S) proportion, the RBM peak was not obtained because Ag2S NPs were not synthesized yet, which can be seen from the XPS results presented in Fig. 2(a). It seems that the amount of Ag2S was too small for the complete synthesis of the NPs. Additionally, with an increase in the proportion of Ag2S, a blue-shift of the G-band and an increase in the intensity ratio of the D and G bands (ID/IG) were observed (Fig. 2(b-iii)). This could be attributed to the increasing density of Ag2S on the CNT surface and the net n-type doping effect of Ag2S NPs on CNTs.28 In the case of the mixture with a 1
:
20 (CNT
:
Ag2S) ratio, the defect concentration increased and a reverse shift from non-bonding Ag2S NPs was observed.
Fig. 2(c) shows the absorption spectra of CNTs, Ag2S, and CNT–ANs. No characteristic absorption peak was observed for CNTs, while a peak of absorption in the 400–500 nm range was recorded for Ag2S NPs and CNT–ANs.29 The charge transfer between Ag2S NPs and CNT–ANs was investigated by photoluminescence (PL) analysis (Fig. 2(d)). Ag2S NPs show a PL emission band at approximately 1264.89 nm, while the CNT–AN films show a relatively low peak intensity than Ag2S. PL emission quenching of Ag2S NPs in CNT–ANs resulted due to the charge transfer from photo-excited Ag2S NPs to CNTs.30 In addition, a remarkable blue-shift of the emission peak was observed at 1210.25 nm for all the films with mixture ratios of 1
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5, 1
:
10, and 1
:
20 (CNT
:
Ag2S) except for the film with the proportion ratio of 1
:
1 (CNT
:
Ag2S), which did not exhibit any PL peak. This blue-shift is explained by the change in the initial electronic density and confinement energy of the Ag2S NPs.31,32
Thin film layers based on CNT–ANs for flexible photodetectors were fabricated by spray-coating on an ultraviolet light-treated SiO2 substrate. Here, the thickness of the CNT–ANs was about 480 nm (Fig. S10 in ESI†). Source/drain electrodes (5 nm Cr/70 nm Au) were deposited on the CNT–ANs film through a shadow mask. The channel length and width of the device were 50 and 500 μm, respectively. The current–voltage (I–V) curve shows the conductivity of each synthesized CNT–ANs film within 1 V (Fig. 3(a)). The curve shows a clear linear response wherein the current of the CNT–ANs film was observed to increase with a corresponding decrease in Ag2S proportions. Fig. 3(b) shows the photocurrent of the fabricated photodetectors based on CNT–ANs under white light exposure. The CNT–ANs device with a 1
:
10 (CNT
:
Ag2S) proportion exhibits the best on-state photocurrent with the recorded value being 26.03 μA. Photoresponsivity (R) of the 1
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10 CNT–Ag2S photodetector with the best photocurrent was calculated by using R = (IPhoto − IDark)/PS, where P is light intensity, S is the illuminated area of the channel. R of our device is 8.3 A W−1 under white light exposure. In addition, the photosensitivity and detectivity were 5.7 × 104 and 1.7 × 1010 Jones, respectively. The value of the gain (G) coefficient at wavelengths of 350, 550, 800 nm were 29.52, 18.78, 12.91, respectively. It is notable that as the wavelength of incident light increases, the gain of photodetectors decreases. Fig. 3(c) exhibits the typical photoresponsivity of CNT–ANs (with a 1
:
10 (CNT
:
Ag2S) proportion) as a function of the source–drain voltage under light exposure with a power density of 12.26 mW cm−2. The observed change of photocurrent with increasing source–drain voltage leads to an increase in the current of the photodetector. The trend continued until the maximum current was reached at a source–drain voltage of 1 V. Fig. S11 in ESI† show the photocurrent in logarithmic scale according to drain voltage. Fig. 3(d) shows a schematic of the energy band alignment with the photodetection mechanism. In the case of nanoscale NPs, the band gap broadening phenomenon can occur because of the strong internal forces to the lattice of the nanoscale materials. Also, Akamatsu et al. showed that the band gap of Ag2S NPs larger than 5 nm almost equal to that of the Ag2S bulk value.33 As mentioned before, the diameter of Ag2S NP in this study was 10 nm, which indicates that there is no quantum confinement effect on NPs and the band gap (Eg) of our Ag2S NP is around 1 eV.34,35 The conduction band minimum (CBM) and valence band maximum (VBM) of Ag2S NPs are taken to be 4.5 and 5.4 eV, respectively.36 The work function of CNTs is in the range of 4.7–4.95.37,38 When the device is exposed to light, photoexcited electrons are transferred from the Ag2S NPs to the CNTs owing to the efficient electron conductivity of the CNTs, which leads to a decrease in the PL intensity.30,31
We obtained the power dependence of the photocurrent of photodetectors based on CNT–ANs with a 1
:
10 (CNT
:
Ag2S) at a source–drain voltage of 1 V under illumination with white light, with light having wavelengths of 800, 550, and 350 nm (Fig. 3(e)-(i and ii)), respectively. The obtained results indicated that the photocurrent changed continuously with the photo-power density, with the best recorded photo-responsivity being 278.22 A W−1 at a wavelength of 800 nm (0.15 mW cm−2) of the NIR light source. This response, displaying an excellent reactivity in the NIR wavelength range, is notably higher than that of the PbS/CNT-based photodetectors reported in previous studies.16,39 This could be ascribed to the excellent absorption characterization of Ag2S NPs in the NIR region.40,41
In this study, CNT–ANs that do not contain heavy metals such as Pb or Cd, were successfully synthesized and applied in the fabrication of flexible and implantable NIR photodetectors. Fig. 3(f)-(i) shows the photo-response of devices based on CNT–ANs with a 1
:
10 (CNT
:
Ag2S) proportion under cyclic illumination with white light and at wavelengths 800, 550, and 350 nm for corresponding power densities of 12.5, 0.38, 0.89, and 1.65 mW cm−2. The recorded photocurrents were observed to be constant for up to 600 s, further confirming the superior performance and stability of the devices. Fig. 3(f)-(ii) shows the response time (τres) and decay time (τdec) under white-light illumination. The measured τres, for which the photocurrent rises from 10 to 90% of maximum, was 1.18 s, while the measured τdec was 15.16 s. Additionally, in cases where the illumination wavelengths were below 800, 550, and 350 nm, the response speed was observed to decrease slightly (Table S1 in ESI†).
To verify the applicability of wearable devices to human skin and the durability of our CNT–AN films for flexible photodetectors, flexible devices based on CNT–ANs were fabricated on a PDMS substrate by spray-coating. The sensing performance was measured according to the bending cycles and bending angles (Fig. 4(a)). In this work, a bending tester (JUNIL TECH Co., LTD-JIBT-610-Radius Bending) was used with a bending radius of 5 mm (Fig. 4(b)). Although the photo-response was relatively reduced because of the quenching effect of the substrate, the photodetection performance remained stable even after 105 bending cycles (Fig. 4(c)). Moreover, the photocurrent maintains almost the same response at high bending angles (0–60°) (Fig. 4(d)).42 This result demonstrates the good mechanical stability of the devices owing to the superior mechanical flexibility characteristic of CNTs. This approach, thus, may pave the way forward for the fabrication of advanced flexible photoelectronic devices.
Footnote |
| † Electronic supplementary information (ESI) available. See DOI: 10.1039/d1ra03385a |
| This journal is © The Royal Society of Chemistry 2021 |