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Abstract
This article delves into the growth and simulation of In0.1Al0.9N/p-Si photodetector devices, focusing on their structural, optical, and electronic properties. The study employs various techniques such as XRD, XPS, HR-TEM, and photoluminescence spectroscopy to characterize the material. Key findings include the high-quality crystal structure of the In0.1Al0.9N alloy, its direct bandgap of 2.94 eV, and its potential for high-performance photodetectors. The article also highlights the use of COMSOL Multiphysics software for simulating the energy band diagram and responsivity of the devices. The results demonstrate the material's suitability for applications in UV photodetection, offering superior detection capabilities and robustness under extreme conditions. This comprehensive analysis provides valuable insights into the material's potential for next-generation optical sensors and imaging systems.
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Abstract
In0.1Al0.9N is a preferred semiconducting compound in the field of photodetection applications, since it has a direct bandgap, which could be controlled by adjusting the percentages of Al and In metals. Here, In0.1Al0.9N is prepared by a simple and low-cost crystal growth methodology on a p-Si substrate. Structural analyses are studied using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and X-ray photoelectron spectroscopy (XPS). Crystallite size, dislocation density, and micro–strain values are calculated according to the three models: Debye–Scherrer, Williamson–Hall (W–H), and Strain Distribution (SD), and their values are compared to each other. The values of optical transitions and energy gap of the fabricated devices are investigated using UV–Vis spectroscopy and photoluminescence techniques. The responsivity and the cut-off wavelength of the fabricated devices are determined using photoresponsivity measurements. A simulation study of the fabricated device is performed to investigate the matching between the simulated data using COMSOL Multiphysics software and the experimentally obtained data. The fabricated device, In0.1Al0.9N/p-silicon, has a great opportunity to be utilized in photodetection applications.
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1 Introduction
Indium Aluminum Nitride (InxAl1-xN) is a promising ternary nitride alloy semiconductor for electronic and optical applications due to its larger localization potential than Aluminum Gallium Nitride (AlxGa1-xN) and Indium Gallium Nitride (InxGa1-xN) [1]. InxAl1-xN has a direct bandgap (Eg) that possesses a broad spectral range from the Indium Nitride (InN) with a narrow bandgap of 0.7 eV [1, 2] to the Aluminum Nitride (AlN) with a wide bandgap of 6.2 eV [3]. InxAl1-xN is widely applied in optoelectronic devices, which possess high luminescent efficiency and operate at various spectral ranges; green and blue emitters of light [3, 4]. They are also utilized in photovoltaics [5], photodetectors [6], and transistors [7, 8]. InxAl1-xN alloy is a so interesting compound due to its potential applications as it could be grown as epitaxial layers. They may be lattice matched [9‐11] or polarized matched [12] to AlGaN or InGaN layers. InxAl1-xN is prepared using different techniques such as molecular beam epitaxy (MBE) [4, 5], radio-frequency metal organic chemical vapor phase epitaxy (MOVPE) [6, 7], and metal organic chemical vapor deposition (MOCVD), which all can yield the nanocolumn structure. The larger localization potential in InxAl1-xN results in stronger carrier confinement, which minimizes carrier leakage and improves quantum efficiency [13]. This makes the InₓAl₁₋ₓN-based photodetectors considered as highly sensitive to low-intensity light and offers superior detection capabilities in harsh or low-visibility environments [14]. Furthermore, the material itself exhibits excellent thermal and chemical stability which is crucial for applications requiring long-term operation under extreme conditions, such as space exploration, environmental monitoring, and biomedical imaging [15, 16]. By leveraging the tunability and robustness of InₓAl₁₋ₓN, advanced photodetectors can be designed to cover a broad range of the electromagnetic spectrum [17, 18]. As a result, InₓAl₁₋ₓN holds significant potential to revolutionize the field of UV photodetection, offering high-performance solutions for next-generation optical sensors and imaging systems [19, 20]. InₓAl₁₋ₓN is a versatile wide bandgap semiconductor with remarkable thermal and chemical stability, which has been extensively investigated for various optoelectronic and energy-related applications. Owing to its tunable bandgap and excellent lattice matching with GaN and AlN, this alloy has been successfully employed in the fabrication of light-emitting diodes (LEDs), high-efficiency laser diodes, solar cells, high electron mobility transistors (HEMTs), Bragg reflectors, photodiodes, ultraviolet detectors, and gas sensing devices [21].
Generally, the preparation of InxAl1-xN thin layers using epitaxial techniques exposes various problems such as high cost, toxic reaction sources, higher fabrication temperatures, the utility of unique substrates with crystalline structure, and the robustness of the equipment. In this study, for photodetectors fabrication, an In0.1Al0.9N nanorod sticks structure is prepared by crystal growth technique “in a tubular furnace” in order to produce the alloyed material and then deposit the alloy on p-Si substrates using spin coating technique. In0.1Al0.9N/Si photodetectors have been modeled using COMSOL Multiphysics software to estimate the energy band diagram and responsivity of InxAl1-xN/p-Si structure as well as the measurement of absorbance bandgap and photoresponsivity of InxAl1-xN/p-Si structure.
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2 Experimental work
2.1 Materials
Aluminum and Indium metals (Sigma-Aldrich) have a purity of 99.99%. An active high-purity atomic nitrogen (99.99%) is supplied from a nitrogen gas supplier. p-Si wafer with a resistance of 1 Ω and a purity of 99.9999% is used as the substrate for deposition of the fabricated InxAl1-xN alloy.
2.2 Synthesis of InxAl1-xN (x = 0.1) alloy by crystal growth method
Indium and Aluminum metals are mixed with (wt%) 0.1 in a ceramic boat to produce In0.1Al0.9N bulk alloys. The temperature growth is held at 900 °C under the flowing of N2 gas. The reaction is started in the tubular furnace (Carbolite TZF 12/75/700 Three Zone Tube Furnace, United Kingdom) at room temperature. The temperature is raised at a rate of 100 °C/30 min until it reaches 900 °C. At 900 °C, the temperature is fixed for 2 h; then it is reduced to 450 °C at the same rate (100 °C/30 min). It is then cooled to ambient temperature normally. The prepared sample is then post-heated at 1200 °C for 2 h in a tubular furnace in N2 gas flow. After the heat treatment step, the produced alloy sample is cooled to 650 °C at a rate of 100 °C/30 min, then left to cool to ambient temperature.
2.3 In0.1Al0.9N thin film fabrication for photodetector application
Spin coating technique (2000 rpm for 1 min (POLOS, USA)) is used in order to deposit a uniform layer of In0.1Al0.9N on p-Si substrate with a dimension of 1 × 2 cm2. Gold metal is deposited as an electrode contact for the optoelectronic measurements (SPI-MODUL CONTROL, USA).
2.4 Characterization tools
The crystalline structure, surface morphology, elemental analysis, and optical properties are investigated. For the crystal structure and surface analysis, two techniques are applied: XRD Shimadzu 7000 diffractometer, Kyoto, Japan, and (XPS) measurements using XPS, SPECS-surface nano analysis GmbH version 4.89.2-r104748, with an X-ray beam source of Al 400 W and a size of 500 μm. For deep morphology and elemental analysis, an HR-TEM “TEM JOEL(JEM-2100, JEOL, Japan) operating at a voltage of 200 kV” is used. For optical properties analysis, photoluminescence properties are characterized to calculate the energy gap of the fabricated nanomaterials with a Luminescence Spectrometer Model LSS from PL-Perkin Elmer. The emitted single photon that has been triggered from the fabricated InxAl1-xN alloy nanostructure is characterized by applying the fluorescence lifetime imaging microscopy (FLIM system Alba with v5 from ISS). A diode laser of wavelength 640 nm (Model IX73, Olympus, Tokyo, Japan) is used as an excitation source. The emission of the samples is detected in a low noise mode with a detector of GaAs [22]. FLIM data are acquired using ISS A330 Fast FLIM module with n harmonics of 20 MHz laser repetition frequency. A simulation study is carried out using COMSOL Multiphysics 5.3 software to estimate the energy band diagram and responsivity of the prepared sample. The prepared device is created as a 2D model using COMSOL Multiphysics 5.3 software. The photodetectors based on the deposited In0.1Al0.9N layer on a p-Si substrate showed high detectivity and photoresponse speed to UV, green, and red light, respectively.
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3 Results and discussion
3.1 The structural analyses
3.1.1 X- ray diffaction
The diffraction patterns of the thin deposited film of the In0.1Al0.9N alloy (x = 0.1) on p-Si substrate using spin coating are shown in Fig. 1. The sample has a polycrystalline structure assigned to hexagonal wurtzite structure, which is considered the most thermodynamically stable phase [23]. The main peaks of In0.1Al0.9N alloy (x = 0.1) are observed between the 2θ values of InN (JCPDS card No. 65–3412) [24] and AlN (JCPDS card No. 653409) [25]. The XRD pattern for small peaks of In0.1Al0.9N corresponding to the direction along (004) at 2θ values of 66.51°, 68.53°, and 71.05° [26], which means that the fabricated nanostructure is oriented in a high direction. There are other peaks at 2θ values of 53.95° and 56.015°, attributed to In0.1Al0.9N are observed along (110) direction [9]. There are also peaks at angles 35.8° and 43.6° along (002) and (102), respectively [9]. As shown, different families of some of the (110) and (101) orientations [14] are observed. This indicates a significant improvement in the structural quality of the fabricated nanostructure, which also appears in the narrow broadening peaks of XRD in the sample. These results indicate a polycrystalline growth of high-quality hexagonal structure. All the diffraction peaks could be assigned to the formation of In0.1Al0.9N single crystal phase. The calculated crystallite size of the particles has an average value of 14.34 nm using Debye–Scherrer’s equation [27]:
where Dhkl is the mean grain size in nm, the wavelength of the characteristics X rays in Å, θ is the bragg diffraction angle in radians, β is the peak full width at half maximum and finally K varies with (hkl) and crystallite shape and here is considered to be 0.94. Also; The density of dislocation (δ) value is calculated by using Eq. (2) [15]:
The microstrain is found to be 7.2 × 10–3. This low value of the microstrain indicates the high structural quality [3].
This smaller crystallite size is expected, since the Debye–Scherrer’s equation attributes all peak broadening to size effects, without the strain contribution [28]. Crystallite size, dislocation density, and average microstrain are calculated using Williamson–Hall equation (Eq. (4)). The value of the crystallite size (D) is obtained from the Y-axis intercept, and the average microstrain is calculated from the slope of the fitting line of the relation between βcosθ versus 4sinθ [28] as shown in Fig. 2.
The Williamson–Hall analysis revealed a crystallite size of 26.7 nm, a microstrain value of 2.55 × 10–5, and a dislocation density of 1.4 × 10–3 nm−2. Unlike the Debye–Scherrer’s equation, the W–H method considers all XRD peaks, lattice strain, and separates their contribution to the peak broadening [29] which explains the larger crystallite size and smaller strain values obtained.
In order to obtain more accurate crystallite size and microstrain values, the Strain Distribution (SD) model is used, which estimates the number of equations about the broadening, peak position, and lattice parameters to determine the crystalline size and strain exponent as follows [30]:
where εx is the microstrain value at position x from the center of the nanoparticle to its surface εmax is the microstrain constant which equal 0.423 (growth of microstrain from center of spherical particle to its surface.
xf* is the reciprocal of the position FWHM and equals 1/xf and is determined using Eq. (7) where k is a constant and wav is an average broadening (= 0.008 rad).
$$x_{f}^{*} = \, k/w_{av}$$
(7)
SD model yielded a crystallite size value of 23.6 nm, close to the W–H result, but revealed a significantly higher average microstrain (εf) value of 0.385 with a dislocation density of 1.8 × 10–3 nm−2. This indicates that the strain is inhomogeneously distributed within the crystallites, due to defects and grain boundaries, which cannot be captured from Debye–Scherrer or Williamson–Hall approaches. Table 1 represents the values of the crystallite size, microstrain, and dislocation density which are obtained from the three models.
Table 1
The calculated parameters (crystallite size, microstrain and dislocation density) Debye–Scherrer, Williamson-Hall (W–H) and Strain Distribution (SD) models
Model
Measurement Equation
Crystallite size
“D” (nm)
Dislocation density
“δ” (nm−2)
Microstrain “ε”
c
Debye–Scherrer
D = kλ/βcosθ
14.34
4.86 × 10−3
0.0072
Williamson–Hall (W–H)
βcosθ = kλ/D + 4εsin
26.71
1.40 × 10−3
2.55 × 10−5
Strain Distribution (SD)
w(2cotθ0—w) = (1.6 × 10–2)(d0/w)-(6.2 × 10–3/c)
23.58
1.8 × 10−3
0.385
0.09
The lattice constant of alloyed In0.1Al0.9N is calculated using Eqs. (4 and 5) depending on the values of a and c of InN and AlN; a = 0.311 nm, c = 0.498 nm [18] for AlN [19], and a = 0.354 nm, c = 0.5706 nm [20] for InN [23] as follows:
So, the value of c/a ratio is 1.603, which is nearly equal to the ideal value (c/a = 1.633) that is in agreement with the value obtained by WC Chen et al. 2014 [24].
3.1.2 X-ray photoelectron spectroscopy (XPS)
Figure 3 shows the XPS measurements of the fabricated In0.1Al0.9N alloy, where the general survey of the sample (Fig. 3a) detects the main elements of the alloy: Al2p with an atomic ratio of 31.9%, In3d with an atomic ratio of 1.09%, and N1s with an atomic ratio of 0.42%. C1s is also detected with an atomic ratio of 18.26%, and O1s with an atomic ratio of 48.31%. The existence of the last two elements may be due to the alloy surface contamination since no oxygen phases are detected in the XRD measurements and low content of the indium in the alloy.
Fig. 3
XPS spectra of In0.1Al0.9N alloy. a General Survey showing peaks of In3d, Al2p, N1s, C1s and O1s; b Al1s and c In1s and d N1s high resolution peaks
Al2p high resolution is shown in Fig. 2b and indicates the existence of two peaks: Al2p1/2 at B.E. of 73.82 eV with an atomic ratio of 77.9% and Al2p3/2 at B.E. of 74.63 eV with an atomic ratio of 22.1% [31‐34]. In Fig. 2c, four peaks of indium content are detected and could be explained as follows: In3d5/2 at 444.1 eV with an atomic ratio of 40.9%, In3d5/2 at 445.2 eV with an atomic ratio of 18.8%, In3d5/2 at 451.8 eV with an atomic ratio of 36.6%, and In3d5/2 at 453.2 eV with an atomic ratio of 3.7%. Finally, N1s high resolution is shown in Fig. 2d with one peak at 400.1 eV. The peaks of Al2p, In2p, and N1s indicate the bonding between Al-N and In-N compounds [32].
3.2 Morphological analysis
Low and high resolution transmission electron microscope images of the synthesized In0.1Al0.9N alloys are shown in Fig. 4a and b, respectively. Sticks of nanorods with a diameter ranging from 12 to 18 nm and a length of 170–250 nm are detected. Low and high resolution TEM micrographs are shown in Fig. 4(c and d). These TEM micrographs indicate a growth of 15–20 nm nanoparticles with a d-spacing of 1.02 nm.
Fig. 4
Transmission electron microscope images of In0.1Al0.9N alloys (a, b), thin film spin coated (c, d), mapping elements distribution; Al (e), In (f), N (j), Mix. (h), and EDX elemental analysis (i)
The crystallite size calculated from the Debye–Scherrer, Williamson–Hall, and strain distribution models is in good agreement with the data determined from the HR-TEM.
The mapping images of Al, In, and N elements (Fig. 4e, f, and j) show regular distribution of the elements into the grains, confirming the good alloying of the compound (Fig. 4h). EDAX analysis indicates a weight ratio of In and Al of 7% and 92%, respectively (as shown in Fig. 4i), which agrees with the starting precursors and XPS results. The produced elemental analysis data is compared with the theoretical atomic percentages of each reactant element as shown in Table 2. The data confirm the stoichiometry of the produced compound and indicate the high quality of the crystal growth technique.
Table 2
EDAX data of produced In0.1Al0.9N
Elements
Theortical atomic ratio (%)
EDAX atomic ratio
In
10
7
Al
90
92
The conversion of the sticks of nanorods onto nanoparticles from the bulk alloys to thin films is previously detected in our previous work of In0.1Ga0.9N [33], which is due to changes in growth environment, surface energy, and film deposition technique which caused the nanorods to transform to nanoparticles, because the surface tension and strain play a larger role in thin films growth [34].
3.3 Optical properties analysis
3.3.1 Photoluminescence
As been known, both the crystal structure and its corresponding quality of the crystallinity for the In0.1Al0.9N alloys are greatly affected by the seedling substrate [9]. This is the first time to use p-Si substrate without depending on the substrate temperature that the published works depend on GaN as its bandgap is compatible with the wide bandgap of In0.1Al0.9N. Therefore, we considered p-Si substrate to be preferable for In0.1Al0.9N film growth by spin coating method.
Figure 5 shows the PL spectrum of the prepared alloy of In0.1Al0.9N nanorod sticks, which is evaluated using an excited laser light beam with wavelength values of 400 nm and 800 nm. The bandgap width (Eg) of In0.1Al0.9N is estimated using Eq. (10) [35]:
where h is Planck’s constant, c is the light velocity and λ (nm) is the wavelength of absorption onset in nm [35]. The calculated bandgap of the prepared In0.1Al0.9N is 2.94 eV which in between the Eg values of InN (0.79 eV) and AlN (6.2 eV) band gaps. The PL spectrum shows a strong photoluminescence (PL) emission peak at a wavelength value of 416 nm. This phenomenon is normally seen in the epitaxial single crystals and the polycrystalline films [36]. This single peak confirm the high quality of the In0.1Al0.9N crystallined structure prepared by crystal growth technique. This sharp band edge emission peak associated with band-to-band emission from the In0.9Al0.1N layers. The energy gap value of InAlN strongly depends on the electrons concentration in the prepared thin films due to Burstein–Moss effect. This means that the energy gap would be increased with higher charge carrier concentration [37].
Fig. 5
Photoluminescence spectrum of the prepared In0.1Al0.9N alloy
For most semiconductor materials, the energy gap, EgAxB1−xN, does not follow a linear Vegard’s law versus the composition, but some degree of deviation is spotted.
This may be referred to the inclusion of a “bowing parameter” b, leading to a parabolic dependence [38]
Estimation of the bowing parameter, b, depends on the sample quality, strain condition, and composition [12, 13]. From the last equation, the bowing parameter is equal to 29.77.
3.3.2 PL time resolved
The optical transitions and the quality of the synthesized In0.1Al0.9N alloy by the crystal growth technique are studied and evaluated using Time-resolved PL. (FLIM) technique is employed to map the spatial distribution lifetime of the nanosecond excited state [39]. Figure 6 shows the temporal response of the localized exciton recombination of In0.1Al0.9N at room temperature. As shown in Fig. 6, the PL decay of In0.1Al0.9N can be described quite well by a single exponential and the PL recombination lifetime is measured at room temperature. The value τau of the sample is about 2.26 ns. This emission lifetime is a characteristic of the localized excitons of semiconductors. In Fig. 6 (the right panel), it shows the phasor plot of the fabricated In0.1Al0.9N alloy. Its intensity decays for the related FLIM image, as shown in Fig. 6 (the left panel). A 2D diagram with two coordinates, namely, S and G, shows every pixel in this image. The s and g coordinates in the phasor plot can be expressed by the following expressions [40];
where fk is the intensity weighted fractional contribution of the component with lifetime τk. ω is the angular frequency of light modulation.
Fig. 6
A The raw FLIM data for In0.1Al0.9N alloy, B The Phasor plots given from the fluorescence FLIM data. C The photoluminescence intensity decay with the fitting curve
The absorbance of the In0.1Al0.9N sample measured using the UV–Vis spectroscopy technique is shown in Fig. 7. The transmittance of the sample is calculated from the relation (Eq. 14):
$${\text{T }} = { 1}0^{{ - {\text{A}}}}$$
(14)
where T is the transmittance and A is the Absorbance [41]. The reflectance of the sample R is estimated using Eq. 15 [42]:
where R∞ is diffuse reflectance of the sample, h is Plank’s constant, Eg is the energy gap, A is a constant, υ is the incident frequency, and n exponent which determines if the transition undergoes indirect (n = 1/2) or the transition undergoes direct (n = 2) according to the linear fitting between hʋ and khʋ.
Figure 8 shows a plot of hʋ versus (khʋ)2. It exhibited a linear fit of the bandgap edge. This means that the sample has a direct energy gap [44] with a value of 2.94 eV, which is the bandgap of In0.1Al0.9N [11]. This matches with the transition value at 2.94 eV, which was measured from PL. The other bandgap value is at 5.51 eV, which corresponds to AlN [45].
Fig. 8
The photoresponsivity of the fabricated In0.1Al0.9N/pSi device
Photoresponsivity of In0.1Al0.9N/pSi device is measured using PVE300 system with 75 W Xenon lamp in a spectral range between 300 and 1600 nm. Figure 8 shows the photoresponsivity of the fabricated In0.1Al0.9N/pSi device. Photoresponsivity measurement shows that the device has spectral response in the UV spectral range with a cut-off wavelength of 448 nm (2.77 eV). The responsivity measurement matches with the absorbance measurement, since the sample has high absorbance in the UV region with a bandgap value of 2.94 eV (according to PL measurement), which mostly agrees with the responsivity cut-off wavelength at 448 nm.
3.4 Simulation study using COMSOL multiphysics 5.3 software
Simulation study is conducted using COMSOL Multiphysics 5.3 software [46] to estimate the energy band diagram and the responsivity of the prepared sample. Frequency Domain interface for semiconductor optoelectronics model is applied for the prepared device. The device is built in a 2D model using COMSOL Multiphysics 5.3 software. It is found that the band diagram and responsivity data obtained from the simulation study match with the experimental data.
Figure 9 shows the energy level diagram of the prepared sample. It is seen that the value of the bandgap valence band edge to conduction band edge is 2.71 eV, which matches with the bandgap value calculated from absorbance measurements using UV–Vis spectroscopy, 2.77 eV.
Fig. 9
Energy level diagram of the prepared In0.1Al0.9N/pSi device using COMSOL Multiphysics software 5.3
To calculate the photo responsivity of the prepared device using the mentioned software, the p-contact is set to 2 V and the n-contact is grounded. Wavelength sweep is performed at the constructed prepared device in the software at a constant power of the incident light in the range from 875 to 50 nm. Figure 10 shows the results of the responsivity of the prepared In0.1Al0.9N prepared device using COMSOL Multiphysics 5.3 software. It is found that the device has a high responsivity value from all over the range of UV spectra to the sharp cut-off wavelength at 500 nm. This cut-off edge meets the value of the simulated and experimental bandgap of the prepared sample. It is about 2.71 eV (459 nm). The experimental results using photoresponsivity data showed that the device has a tailed cut-off wavelength at ≈ 400 nm. The difference between the experimental tailed cut-off wavelength and the theoretical sharp cut-off wavelength is due to the fact that the COMSOL Multiphysics 5.3 software material library uses single crystalline material that has a perfect sharp cut-off. Another reason is that this module of the software uses a constant power of the incident light all over the range of the incident spectrum on the constructed device. On the other hand, the experimentally prepared sample has multiorientation of crystallites growth [47, 48].
Fig. 10
Responsivity of the fabricated In0.1Al0.9N/pSi device using COMSOL Multiphysics 5.3 software
In0.1Al0.9N nanostructure alloy is grown using a crystal growth technique and its thin film is prepared by a low-cost spin coating technique. HR-TEM analysis revealed that the grown In0.1Al0.9N has a like nanorod stick structure. XRD data showed a high-quality crystal structure, which minimized the defects and directly influenced the responsivity and detection efficiency. Time-resolved PL showed a high value of the charge carrier lifetime of the prepared device to be 2.26 ns. UV–Vis spectroscopy measurements showed a direct bandgap of the prepared In0.1Al0.9N. The value of the energy gap is estimated using UV–Vis spectroscopy and photoluminescence measurements, which lies between 2.77 and 2.94 eV, respectively. Simulation data from COMSOL Multiphysics 5.3 software showed that the value of the bandgap valence band edge to the conduction band edge is 2.71 eV which matches with the value of the bandgap obtained from absorbance measurements using UV–Vis spectroscopy. The experimental results using Photoresponsivity data showed that the device has photoresponsivity in the UV and visible region with a tailed cut-off wavelength at ≈ 400 nm which matches to some extent with the simulation data. This gives the prepared device greater opportunity to be used in photodetection applications.
Acknowledgments
This work was carried out at City of Scientific Research and Technological Applications (SRTA-City) and collaboration research with the Faculty of Science, Menoufia University. The PL time-resolved characterization is measured by the National Research Center (NRC) (Prof. Badawi Anis).
Declarations
Conflict of interest
The authors declare that they have no conflict of interest.
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