- Email: [email protected]
Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications
Journal Pre-proofs Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications P.M. Jayasankar, Amit Kumar Pathak, Sreejith P. Madhusudanan, Sunjay Murali, Sudip K. Batabyal PII: DOI: Reference:
S0167-577X(19)31832-4 https://doi.org/10.1016/j.matlet.2019.127200 MLBLUE 127200
To appear in:
Materials Letters
Received Date: Accepted Date:
7 November 2019 18 December 2019
Please cite this article as: P.M. Jayasankar, A. Kumar Pathak, S.P. Madhusudanan, S. Murali, S.K. Batabyal, Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications, Materials Letters (2019), doi: https://doi.org/10.1016/j.matlet.2019.127200
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
© 2019 Published by Elsevier B.V.
Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications Jayasankar P M[a], Amit Kumar Pathak [b], Sreejith P Madhusudanan [b], Sunjay Murali[a] , Sudip K Batabyal[b]*
_______________________________________________________ [a]
Department of Sciences, Amrita School of Engineering, Coimbatore
Amrita Vishwa Vidyapeetham, Tamil Nadu 641112, India [b]
Amrita Centre for Industrial Research & Innovation (ACIRI), Amrita School of Engineering, Amrita
Vishwa Vidyapeetham, Coimbatore, Tamil Nadu 641112, India Email: [email protected]; [email protected]
1
Abstract Recently reported double perovskites (DPs), Cs4CuSb2Cl12 has led to the development of a new lead free perovskite. It is 1 eV band gap material. The perovskite microcrystals were synthesized via liquid phase method. This was investigated as active solar energy materials for visible-light photodetector. The microcrystalline device was made in a single-step printable Cs4CuSb2Cl12/carbon materials composite paste. 10 wt % active material composite was found to be the best candidate for the highest responsivity, 10 ―3 A/W and detectivity, 108J. One-step printing of the composite paste can be used for cost effective photodetector applications. Keywords Solar energy materials, Double Perovskite; Cesium Copper Antimony Chloride (Cs4CuSb2Cl12); Carbon materials; Photodetector. Introduction Recently, organic-inorganic lead halide perovskites emerged as solar energy materials having low cost and exhibits high power-conversion efficiency (from 3.8 % to 22 %) [1-4]. Based on composition, they showcase a mystifying set of alluring properties, including superconductivity, spintronics and catalytic properties. Perovskites, therefore, have ended up being an interesting branch of investigation for physicists, material scientists and chemists alike. Although perovskite absorber layer is deposited by means of a simple solution processed methods, whereas the electrodes and the charge collection layer deposition need expensive materials and complex technologies. Therefore, in order to reduce costs for device fabrication, carbon materials with excellent stability and conductivity can be utilized as electrodes [5]. Over the years, the application of several perovskite materials have been investigated with a general consensus that leadbased perovskites have the edge in several photoelectric and physical properties under consideration [6]. However, hybrid lead perovskites face challenges in commercial implementation due to toxicity of lead and poor thermal, photo and moisture stability. In this regard, numerous efforts have been put forward to replace lead in perovskite technology [7, 8]. Researchers sought to expand on the lead-free perovskites, and perovskite like materials such as SbSI, and BiI3 which could replace lead perovskites in the long run [9,10]. A majority of double perovskites shows indirect band gap and the one that have direct band gap having large optical band gap like Cs3Sb2Cl9 (3 eV) [11]. To overcome the difficulties, a proposed compound Cs4CuSb2Cl12 utilizes the substitution of Pb2+ by Cu2+ and Sb3+ has been investigated [12-14].
2
Cs4CuSb2Cl12, a triple layered perovskite formed by interlocking octahedrons of Sb2+ and Cu2+, was first reported in 2017 to have a band gap of 1 eV and showed promise for photovoltaic applications [13]. Having a structure that resembles Cs4Sb2Cl9, it can be thought of as having a CuCl6 octahedron sandwiched between layers of SnCl6 [12]. Being devoid of lead, this complex perovskite showed great photo and thermal stability and might well be the forerunner in dethroning methylammonium lead halides as the next great perovskite material. Our work sets out to investigate the viability of Cs4CuSb2Cl12 perovskite in carbon matrix for photodetector applications. 2. Experimental Cesium chloride (99.9%, Sigma-Aldrich), antimony chloride (99.9%, Aldrich), copper chloride dihydrate (99.0%, Sigma-Aldrich) were used in the synthesis. Cs4CuSb2Cl12 microcrystals were prepared by mixing CsCl (10 mmol), SbCl3 (5 mmol) and CuCl2 (2.5 mmol) in adequate amounts of ethanol at room temperature under stirring [14]. The mixture was immediately turned to black precipitate which was filtered and dried. The devices were fabricated by depositing 1 cm2 active area of a single-step printable paste across a thermally coated Al electrodes on a glass substrate [15]. The varying weight percentages of the photoactive material along with 2:1 weight ratio of activated carbon and graphite in Dimethylformamide was tested for its photovoltaic applications. 3. Results and discussion The morphology and microstructure of the synthesised Cs4CuSb2Cl12 crystals are shown in Fig. 1(a) and indicates 3-D microcrystal formation with a large variation in crystal size ranging from 2 µm to 10 µm. The crystal morphology suggests a layer by layer formation mechanism which could be utilised to further reduce the size of the particles or even achieve a two dimensional crystal structure. Elemental mapping shows Cu situated deep into the material (Fig. S2). This gives Cu deficit stoichiometric formation of the compound in EDXs (Fig. S1).
3
Fig. 1. (a) FESEM image, (b) XRD pattern, (c) FTIR and (d) Tauc plot of Cs4CuSb2Cl12 powder crystals. Fig. 1(b) shows the XRD pattern of synthesised sample confirming that the black powdered crystals match the reported monoclinic C2/m space group Cs4CuSb2Cl12 micro crystals [13]. The FTIR result of the sample has been displayed as Fig. 1(c) and includes metal-halide stretching at 617.75 cm-1. Optical properties of Cs4CuSb2Cl12 were studied using the absorption studies as shown in Fig. S3 absorbance values were low but displayed sustained photoactivity. Tauc plot determines the direct band gap, which was calculated to be 1.16 eV as seen in Fig. 1(d). The TGA analysis is shown in Fig. S4 which clearly indicates a massive change in mass of the sample from 240 °C implying a breakage of the layered perovskite structure into SbCl3, Cs3Sb2Cl9 and Cs2CuCl4 [14]. Due to the acceptable stability up to this temperature, there can be a wide range of devices that can utilise Cs4CuSb2Cl12. The stability of these powder crystals are confined from TGA analysis as it can observed that 50% of the sample is being lost only after 600 0C of heat treatment. The device was constructed using carbon matrix as a hole transport material [13]. Fig. 2 (a) shows the (I-V) characteristic of the Cs4CuSb2Cl12 device for bias voltages from -2 to 2 V with there being an asymmetric response across the first and third quadrants. It shows that 10 wt % seems to be the most efficient at photo-generation in this arrangement followed by 5 and 15 wt % (Fig. S5).
4
𝐼𝑙𝑖𝑔ℎ𝑡
Fig. 2. (a) I-V curves of 10 wt % of active material in carbon matrix, (b) 𝐼𝑑𝑎𝑟𝑘 ratio of 5, 10, 15 and 20 wt % samples in carbon matrix (c) Response-current taken at zero bias voltage (d) Detailed view of one modulation cycle, showing the rise-time τr and fall-time (decay time) τd. Fig. 2(a) shows that the device having 10 wt % produces highest photocurrent and photocurrent per dark current in the system. The plot for different weight percentages (5, 10, 15 and 20 wt %) versus the light to dark ratio is shown in Fig. 2(b). Fig. 2(c) demonstrates that due to the lack of bias applied, even though the current boosting abilities of the carbon matrix were reduced, the photodetector shows considerable current at zero volts. The rise time, which was calculated to be τr = 120 ms for the device, the fall time is seen to be τd = 180 ms from Fig. 2(d). Fig. 3(a) shows the (I-V) plot for a device of 10 wt % at varying intensities from 0.0711 W/cm2 to 0.197 W/cm2 which shows an increase in current. Fig. 3(b) plots the responsivity (R) of the device against irradiance using the equation [16]:
5
𝑅 =
𝐼𝐿𝑖𝑔ℎ𝑡 ― 𝐼𝐷𝑎𝑟𝑘 𝐸𝑖 𝐴
Where ‘𝐼𝐿𝑖𝑔ℎ𝑡 and 𝐼𝐷𝑎𝑟𝑘’ are current generated in the presence of light and absence of light respectively and ‘A’ is the active area of the device observed to be 1cm2. The reducing trend with increasing in irradiance suggests that not all the photons are being utilized in higher intensity incidence instances. The ability of a photodetector to detect small signals is measured by the specific detectivity (Ds) and assuming the noise in the system is dominated by the dark current, it can be written as [16]: 𝐷𝑠 =
𝐴𝑅 2𝑒𝐼𝐷𝑎𝑟𝑘
Where ‘e’ is charge on an electron. Specific detectivity has the derived unit Jones (1J = 1 cm W-1 s-0.5) and it is observed that the device fabricated has Ds of the order of 108 J as seen in Fig. 3(c). Fig. 3(d) shows a clear increase in Signal-to-noise ratio (SNR) for the device at 10 wt % versus irradiance from 20 at 0.0711 W/cm2 to 45 at 0.195 W/cm2. This was calculated from the equation [16]: 𝑆𝑁𝑅 =
𝐼𝐿𝑖𝑔ℎ𝑡 ― 𝐼𝐷𝑎𝑟𝑘 𝐼𝐷𝑎𝑟𝑘
6
Fig 3: (a) I-V curve for varying intensities, (b) Irradiance vs. SNR, (c) Irradiance vs. responsivity and (d) Irradiance vs. specific detectivity for 10 wt % in carbon matrix device. 4. Conclusions The viability of Cs4CuSb2l12 in photodetector applications in a carbon matrix has been investigated. 10 wt % of the active material carbon composite paste attained a fast response time of 120 ms, specific detectivity of the order of 108 J, responsivity of the order of 10-3 A/W and a signal-to-noise ratio of one order of magnitude. Being a layered perovskite structure and 1 eV band gap material, Cs4CuSb2l12 can be tailored for its desired applications. Acknowledgement The authors acknowledge Science and Engineering Research Board (SERB) of the Department of Science and Technology (DST) (Research Grant ECR/2015/000208) for financial support. References
[1] Kojima A, Teshima K, Shirai Y, Miyasaka T, Organometal Halide Perovskites as Visible-Light
Sensitizers for Photovoltaic Cells, J Am Chem Soc. 131 (2009) 6050–6051. [2] Murali S, Madhusudanan SP, Pathak AK, Jayasankar PM, Batabyal SK, Carbon Assisted
Methylammonium Lead Iodide Microcrystalline device for an Inexpensive Self-Powered Photodetector, Mater. Lett. 254 (2019) 428-432. [3] Lee MM, Teuscher J, Miyasaka T, Murakami TN, Snaith HJ, Efficient hybrid solar cells based on
meso-superstructured organometal halide perovskites, Science. 338 (2012) 643-647. [4] Manser JS, Christians JA, Kamat PV, Intriguing optoelectronic properties of metal halide
perovskites, Chem. Rev. 116 (2016) 12956-13008. [5] Li Z, Kulkarni SA, Boix PP, Shi E, Cao A, Fu K, Batabyal SK, Zhang J, Xiong Q, Wong LH,
Mathews N, Laminated carbon nanotube networks for metal electrode-free efficient perovskite solar cells, ACS nano. 8 (2014) 6797-6804. [6] Vasala S, Karppinen M, A2B′B″O6 perovskites: a review, Prog Solid State Chem. 43 (2015) 1-36. [7] Hao F, Stoumpos CC, Cao DH, Chang RP, Kanatzidis MG, Lead-free solid-state organic–
inorganic halide perovskite solar cells, Nat. Photon. 8 (2014) 489. [8] Ganose AM, Savory CN, Scanlon DO, Beyond methylammonium lead iodide: prospects for the
emergent field of ns2 containing solar absorbers, Chem. Comm. 53 (2017) 20-44.
7
[9] Pathak AK, Prasad MD, Batabyal SK, One-dimensional SbSI crystals from Sb, S, and I mixtures
in ethylene glycol for solar energy harvesting, Appl. Phys. A. 125 (2019) 213 [10] Prasad MD, Sangani LV, Batabyal SK, Krishna MG, Single and twinned
plates of 2D layered
BiI3 for use as nanoscale pressure sensors, Cryst. Eng. Comm. 20 (2018) 4857-4866 [11] Shi Z, Jayatissa A, Perovskites-based solar cells: A review of recent progress, materials and
processing methods, Materials. 11 (2018) 729 [12] Vargas B, Ramos E, Pérez-Gutiérrez E, Alonso JC, Solis-Ibarra D, A Direct Bandgap Copper–
Antimony Halide Perovskite, J. Am. Chem. Soc. 139 (2017) 9116-9119 [13] Karmakar A, Dodd MS, Agnihotri S, Ravera E, Michaelis VK, Cu (II)-Doped Cs2SbAgCl6
Double Perovskite: A Lead-Free, Low-Bandgap Material, Chem. Mater. 30 (2018) 8280-8290 [14] Wang XD, Miao NH, Liao JF, Li WQ, Xie Y, Chen J, Sun ZM, Chen HY, Kuang DB, The top-
down
synthesis
of
single-layered
Cs4CuSb2Cl12
halide
perovskite
nanocrystals
for
photoelectrochemical application, Nanoscale. 11 (2019) 5180-5187. [15] Madhusudanan SP, Krishna OV, Mohanta K, Batabyal SK, Lead Iodide Microcrystals in Carbon
Composite Matrix for Low Power Photodetectors, ChemistrySelect. 2 (2017) 11025-11029. [16] Driggers RG, Encyclopedia of Optical Engineering:Las-Pho, CRC press. 2 (2003) 1025-2048.
8
Conflict of interest The authors declared that they have no conflicts of interest to this work.
Highlight: 1. Double perovskites Cs4CuSb2Cl12 microcrystals were synthesised by simple solution method. 2. Photoresponsive composite carbon paste was fabricated by mixing carbon and perovskites Cs4CuSb2Cl12 microcrystals. 3. Self powered photodetector were fabricated by single step printed method.
[17]
9
S0167-577X(19)31832-4 https://doi.org/10.1016/j.matlet.2019.127200 MLBLUE 127200
To appear in:
Materials Letters
Received Date: Accepted Date:
7 November 2019 18 December 2019
Please cite this article as: P.M. Jayasankar, A. Kumar Pathak, S.P. Madhusudanan, S. Murali, S.K. Batabyal, Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications, Materials Letters (2019), doi: https://doi.org/10.1016/j.matlet.2019.127200
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
© 2019 Published by Elsevier B.V.
Double perovskite Cs4CuSb2Cl12 microcrystalline device for cost effective photodetector applications Jayasankar P M[a], Amit Kumar Pathak [b], Sreejith P Madhusudanan [b], Sunjay Murali[a] , Sudip K Batabyal[b]*
_______________________________________________________ [a]
Department of Sciences, Amrita School of Engineering, Coimbatore
Amrita Vishwa Vidyapeetham, Tamil Nadu 641112, India [b]
Amrita Centre for Industrial Research & Innovation (ACIRI), Amrita School of Engineering, Amrita
Vishwa Vidyapeetham, Coimbatore, Tamil Nadu 641112, India Email: [email protected]; [email protected]
1
Abstract Recently reported double perovskites (DPs), Cs4CuSb2Cl12 has led to the development of a new lead free perovskite. It is 1 eV band gap material. The perovskite microcrystals were synthesized via liquid phase method. This was investigated as active solar energy materials for visible-light photodetector. The microcrystalline device was made in a single-step printable Cs4CuSb2Cl12/carbon materials composite paste. 10 wt % active material composite was found to be the best candidate for the highest responsivity, 10 ―3 A/W and detectivity, 108J. One-step printing of the composite paste can be used for cost effective photodetector applications. Keywords Solar energy materials, Double Perovskite; Cesium Copper Antimony Chloride (Cs4CuSb2Cl12); Carbon materials; Photodetector. Introduction Recently, organic-inorganic lead halide perovskites emerged as solar energy materials having low cost and exhibits high power-conversion efficiency (from 3.8 % to 22 %) [1-4]. Based on composition, they showcase a mystifying set of alluring properties, including superconductivity, spintronics and catalytic properties. Perovskites, therefore, have ended up being an interesting branch of investigation for physicists, material scientists and chemists alike. Although perovskite absorber layer is deposited by means of a simple solution processed methods, whereas the electrodes and the charge collection layer deposition need expensive materials and complex technologies. Therefore, in order to reduce costs for device fabrication, carbon materials with excellent stability and conductivity can be utilized as electrodes [5]. Over the years, the application of several perovskite materials have been investigated with a general consensus that leadbased perovskites have the edge in several photoelectric and physical properties under consideration [6]. However, hybrid lead perovskites face challenges in commercial implementation due to toxicity of lead and poor thermal, photo and moisture stability. In this regard, numerous efforts have been put forward to replace lead in perovskite technology [7, 8]. Researchers sought to expand on the lead-free perovskites, and perovskite like materials such as SbSI, and BiI3 which could replace lead perovskites in the long run [9,10]. A majority of double perovskites shows indirect band gap and the one that have direct band gap having large optical band gap like Cs3Sb2Cl9 (3 eV) [11]. To overcome the difficulties, a proposed compound Cs4CuSb2Cl12 utilizes the substitution of Pb2+ by Cu2+ and Sb3+ has been investigated [12-14].
2
Cs4CuSb2Cl12, a triple layered perovskite formed by interlocking octahedrons of Sb2+ and Cu2+, was first reported in 2017 to have a band gap of 1 eV and showed promise for photovoltaic applications [13]. Having a structure that resembles Cs4Sb2Cl9, it can be thought of as having a CuCl6 octahedron sandwiched between layers of SnCl6 [12]. Being devoid of lead, this complex perovskite showed great photo and thermal stability and might well be the forerunner in dethroning methylammonium lead halides as the next great perovskite material. Our work sets out to investigate the viability of Cs4CuSb2Cl12 perovskite in carbon matrix for photodetector applications. 2. Experimental Cesium chloride (99.9%, Sigma-Aldrich), antimony chloride (99.9%, Aldrich), copper chloride dihydrate (99.0%, Sigma-Aldrich) were used in the synthesis. Cs4CuSb2Cl12 microcrystals were prepared by mixing CsCl (10 mmol), SbCl3 (5 mmol) and CuCl2 (2.5 mmol) in adequate amounts of ethanol at room temperature under stirring [14]. The mixture was immediately turned to black precipitate which was filtered and dried. The devices were fabricated by depositing 1 cm2 active area of a single-step printable paste across a thermally coated Al electrodes on a glass substrate [15]. The varying weight percentages of the photoactive material along with 2:1 weight ratio of activated carbon and graphite in Dimethylformamide was tested for its photovoltaic applications. 3. Results and discussion The morphology and microstructure of the synthesised Cs4CuSb2Cl12 crystals are shown in Fig. 1(a) and indicates 3-D microcrystal formation with a large variation in crystal size ranging from 2 µm to 10 µm. The crystal morphology suggests a layer by layer formation mechanism which could be utilised to further reduce the size of the particles or even achieve a two dimensional crystal structure. Elemental mapping shows Cu situated deep into the material (Fig. S2). This gives Cu deficit stoichiometric formation of the compound in EDXs (Fig. S1).
3
Fig. 1. (a) FESEM image, (b) XRD pattern, (c) FTIR and (d) Tauc plot of Cs4CuSb2Cl12 powder crystals. Fig. 1(b) shows the XRD pattern of synthesised sample confirming that the black powdered crystals match the reported monoclinic C2/m space group Cs4CuSb2Cl12 micro crystals [13]. The FTIR result of the sample has been displayed as Fig. 1(c) and includes metal-halide stretching at 617.75 cm-1. Optical properties of Cs4CuSb2Cl12 were studied using the absorption studies as shown in Fig. S3 absorbance values were low but displayed sustained photoactivity. Tauc plot determines the direct band gap, which was calculated to be 1.16 eV as seen in Fig. 1(d). The TGA analysis is shown in Fig. S4 which clearly indicates a massive change in mass of the sample from 240 °C implying a breakage of the layered perovskite structure into SbCl3, Cs3Sb2Cl9 and Cs2CuCl4 [14]. Due to the acceptable stability up to this temperature, there can be a wide range of devices that can utilise Cs4CuSb2Cl12. The stability of these powder crystals are confined from TGA analysis as it can observed that 50% of the sample is being lost only after 600 0C of heat treatment. The device was constructed using carbon matrix as a hole transport material [13]. Fig. 2 (a) shows the (I-V) characteristic of the Cs4CuSb2Cl12 device for bias voltages from -2 to 2 V with there being an asymmetric response across the first and third quadrants. It shows that 10 wt % seems to be the most efficient at photo-generation in this arrangement followed by 5 and 15 wt % (Fig. S5).
4
𝐼𝑙𝑖𝑔ℎ𝑡
Fig. 2. (a) I-V curves of 10 wt % of active material in carbon matrix, (b) 𝐼𝑑𝑎𝑟𝑘 ratio of 5, 10, 15 and 20 wt % samples in carbon matrix (c) Response-current taken at zero bias voltage (d) Detailed view of one modulation cycle, showing the rise-time τr and fall-time (decay time) τd. Fig. 2(a) shows that the device having 10 wt % produces highest photocurrent and photocurrent per dark current in the system. The plot for different weight percentages (5, 10, 15 and 20 wt %) versus the light to dark ratio is shown in Fig. 2(b). Fig. 2(c) demonstrates that due to the lack of bias applied, even though the current boosting abilities of the carbon matrix were reduced, the photodetector shows considerable current at zero volts. The rise time, which was calculated to be τr = 120 ms for the device, the fall time is seen to be τd = 180 ms from Fig. 2(d). Fig. 3(a) shows the (I-V) plot for a device of 10 wt % at varying intensities from 0.0711 W/cm2 to 0.197 W/cm2 which shows an increase in current. Fig. 3(b) plots the responsivity (R) of the device against irradiance using the equation [16]:
5
𝑅 =
𝐼𝐿𝑖𝑔ℎ𝑡 ― 𝐼𝐷𝑎𝑟𝑘 𝐸𝑖 𝐴
Where ‘𝐼𝐿𝑖𝑔ℎ𝑡 and 𝐼𝐷𝑎𝑟𝑘’ are current generated in the presence of light and absence of light respectively and ‘A’ is the active area of the device observed to be 1cm2. The reducing trend with increasing in irradiance suggests that not all the photons are being utilized in higher intensity incidence instances. The ability of a photodetector to detect small signals is measured by the specific detectivity (Ds) and assuming the noise in the system is dominated by the dark current, it can be written as [16]: 𝐷𝑠 =
𝐴𝑅 2𝑒𝐼𝐷𝑎𝑟𝑘
Where ‘e’ is charge on an electron. Specific detectivity has the derived unit Jones (1J = 1 cm W-1 s-0.5) and it is observed that the device fabricated has Ds of the order of 108 J as seen in Fig. 3(c). Fig. 3(d) shows a clear increase in Signal-to-noise ratio (SNR) for the device at 10 wt % versus irradiance from 20 at 0.0711 W/cm2 to 45 at 0.195 W/cm2. This was calculated from the equation [16]: 𝑆𝑁𝑅 =
𝐼𝐿𝑖𝑔ℎ𝑡 ― 𝐼𝐷𝑎𝑟𝑘 𝐼𝐷𝑎𝑟𝑘
6
Fig 3: (a) I-V curve for varying intensities, (b) Irradiance vs. SNR, (c) Irradiance vs. responsivity and (d) Irradiance vs. specific detectivity for 10 wt % in carbon matrix device. 4. Conclusions The viability of Cs4CuSb2l12 in photodetector applications in a carbon matrix has been investigated. 10 wt % of the active material carbon composite paste attained a fast response time of 120 ms, specific detectivity of the order of 108 J, responsivity of the order of 10-3 A/W and a signal-to-noise ratio of one order of magnitude. Being a layered perovskite structure and 1 eV band gap material, Cs4CuSb2l12 can be tailored for its desired applications. Acknowledgement The authors acknowledge Science and Engineering Research Board (SERB) of the Department of Science and Technology (DST) (Research Grant ECR/2015/000208) for financial support. References
[1] Kojima A, Teshima K, Shirai Y, Miyasaka T, Organometal Halide Perovskites as Visible-Light
Sensitizers for Photovoltaic Cells, J Am Chem Soc. 131 (2009) 6050–6051. [2] Murali S, Madhusudanan SP, Pathak AK, Jayasankar PM, Batabyal SK, Carbon Assisted
Methylammonium Lead Iodide Microcrystalline device for an Inexpensive Self-Powered Photodetector, Mater. Lett. 254 (2019) 428-432. [3] Lee MM, Teuscher J, Miyasaka T, Murakami TN, Snaith HJ, Efficient hybrid solar cells based on
meso-superstructured organometal halide perovskites, Science. 338 (2012) 643-647. [4] Manser JS, Christians JA, Kamat PV, Intriguing optoelectronic properties of metal halide
perovskites, Chem. Rev. 116 (2016) 12956-13008. [5] Li Z, Kulkarni SA, Boix PP, Shi E, Cao A, Fu K, Batabyal SK, Zhang J, Xiong Q, Wong LH,
Mathews N, Laminated carbon nanotube networks for metal electrode-free efficient perovskite solar cells, ACS nano. 8 (2014) 6797-6804. [6] Vasala S, Karppinen M, A2B′B″O6 perovskites: a review, Prog Solid State Chem. 43 (2015) 1-36. [7] Hao F, Stoumpos CC, Cao DH, Chang RP, Kanatzidis MG, Lead-free solid-state organic–
inorganic halide perovskite solar cells, Nat. Photon. 8 (2014) 489. [8] Ganose AM, Savory CN, Scanlon DO, Beyond methylammonium lead iodide: prospects for the
emergent field of ns2 containing solar absorbers, Chem. Comm. 53 (2017) 20-44.
7
[9] Pathak AK, Prasad MD, Batabyal SK, One-dimensional SbSI crystals from Sb, S, and I mixtures
in ethylene glycol for solar energy harvesting, Appl. Phys. A. 125 (2019) 213 [10] Prasad MD, Sangani LV, Batabyal SK, Krishna MG, Single and twinned
plates of 2D layered
BiI3 for use as nanoscale pressure sensors, Cryst. Eng. Comm. 20 (2018) 4857-4866 [11] Shi Z, Jayatissa A, Perovskites-based solar cells: A review of recent progress, materials and
processing methods, Materials. 11 (2018) 729 [12] Vargas B, Ramos E, Pérez-Gutiérrez E, Alonso JC, Solis-Ibarra D, A Direct Bandgap Copper–
Antimony Halide Perovskite, J. Am. Chem. Soc. 139 (2017) 9116-9119 [13] Karmakar A, Dodd MS, Agnihotri S, Ravera E, Michaelis VK, Cu (II)-Doped Cs2SbAgCl6
Double Perovskite: A Lead-Free, Low-Bandgap Material, Chem. Mater. 30 (2018) 8280-8290 [14] Wang XD, Miao NH, Liao JF, Li WQ, Xie Y, Chen J, Sun ZM, Chen HY, Kuang DB, The top-
down
synthesis
of
single-layered
Cs4CuSb2Cl12
halide
perovskite
nanocrystals
for
photoelectrochemical application, Nanoscale. 11 (2019) 5180-5187. [15] Madhusudanan SP, Krishna OV, Mohanta K, Batabyal SK, Lead Iodide Microcrystals in Carbon
Composite Matrix for Low Power Photodetectors, ChemistrySelect. 2 (2017) 11025-11029. [16] Driggers RG, Encyclopedia of Optical Engineering:Las-Pho, CRC press. 2 (2003) 1025-2048.
8
Conflict of interest The authors declared that they have no conflicts of interest to this work.
Highlight: 1. Double perovskites Cs4CuSb2Cl12 microcrystals were synthesised by simple solution method. 2. Photoresponsive composite carbon paste was fabricated by mixing carbon and perovskites Cs4CuSb2Cl12 microcrystals. 3. Self powered photodetector were fabricated by single step printed method.
[17]
9