The halide perovskites are a family of semiconductor ionic materials possessing unique photoactive, optoelectronic and photonic properties. The first halide perovskite light-emitting diode (PeLED) was demonstrated in the early 90’s
Opto-Electronic Advances, Volume. 6, Issue 9, 220154(2023)
ITO-free silicon-integrated perovskite electrochemical cell for light-emission and light-detection
Halide perovskite light-emitting electrochemical cells are a novel type of the perovskite optoelectronic devices that differs from the perovskite light-emitting diodes by a simple monolayered architecture. Here, we develop a perovskite electrochemical cell both for light emission and detection, where the active layer consists of a composite material made of halide perovskite microcrystals, polymer support matrix, and added mobile ions. The perovskite electrochemical cell of CsPbBr3:PEO:LiTFSI composition, emitting light at the wavelength of 523 nm, yields the luminance more than 7000 cd/m2 and electroluminescence efficiency of 1.3×105 lm/W. The device fabricated on a silicon substrate with transparent single-walled carbon nanotube film as a top contact exhibits 40% lower Joule heating compared to the perovskite optoelectronic devices fabricated on conventional ITO/glass substrates. Moreover, the device operates as a photodetector with a sensitivity up to 0.75 A/W, specific detectivity of 8.56×1011 Jones, and linear dynamic range of 48 dB. The technological potential of such a device is proven by demonstration of 24-pixel indicator display as well as by successful device miniaturization by creation of electroluminescent images with the smallest features less than 50 μm.
Introduction
The halide perovskites are a family of semiconductor ionic materials possessing unique photoactive, optoelectronic and photonic properties. The first halide perovskite light-emitting diode (PeLED) was demonstrated in the early 90’s
Figure 1.Schematic diagrams of (
The alternative to PeLEDs in light-emitting devices field of research is perovskite light-emitting electrochemical cells (PeLECs). In contrast to a conventional PeLED multilayered structure, PeLEC consists of a single multifunctional layer
In a typical PeLEC structure
One of the significant issues in PeLEDs and PeLECs application for display design is Joule heating poor endurance of conventional substrates (soda-lime glass, polyethylene terephthalate (PET), etc.)
Finally, expanding the functionalities of halogen perovskite devices
Here we demonstrate PeLEC device consisting of a single layer of composite inorganic perovskite material, i.e. CsPbBr3:PEO:LiTFSI mixture. In contrast to all previously reported advances
Moreover, in this work, we discuss the technological potential of perovskite materials integration into the CMOS process by demonstrating the PeLEC/n-Si++ indicator display with individual pixels independent addressing and the successful PeLEC device miniaturization. Previously, there were reports of perovskite displays with individual pixels addressing
Material and methods
Silicon substrate processing.
We used phosphorous-doped single-crystal silicon substrates <100> (n ++-Si(100), ρ < 0.005 Ohm∙cm) for device fabrication. Firstly, we formed a 200 nm thick silicon dioxide (SiO 2) layer on the surface of the Si substrate via thermal oxidation. Secondly, the substrate was cut into ~2×2 cm samples. Then, a positive photoresist AZ MIR 701 (MicroChemicals GmbH) (film thickness ~ 860 nm) was spin-coated onto the SiO2/Si side of each sample for photolithography. To fabricate the device area (pixels with 2×2 mm2 in size), we patterned the photoresist with a laser lithography system Heidelberg Instruments Mikrotechnik DWL 66 FS setup. After that, the photoresist was being developed for 1 minute in AZ 726 MIF developer (MicroChemicals GmbH), washed away afterwards by deionized water and dried with nitrogen flow. Next, we etched away the SiO2 insulating layer through the patterned photoresist mask with hydrofluoric acid (HF). The residual photoresist was removed using the organic solvent dimethyl sulfoxide (DMSO). The substrate was then washed in deionized water. As a result, an insulating layer of SiO2 with etched areas was formed on the Si substrate. Finally, bottom aluminum (Al, thickness ~ 200 nm) contact was deposited on the back side of the pre-processed n++-Si(100) substrate by vacuum thermal evaporation in the Boc Edwards Auto 500 set-up at 9×10−6 mbar pressure (1 bar=100 kPa). The Si substrate processing scheme is given in
Figure 2.(
Composite perovskite solution preparation and layer formation
To make perovskite solution of 0.2 molar concentration cesium bromide (CsBr) salt (99.99% purity, Lankhit) was mixed with lead(II) bromide salt (99.99% purity, Lankhit) in a 1∶1 molar ratio, then dissolved in dimethyl sulfoxide (DMSO) (anhydrous DMSO 99.8%, Sigma Aldrich) at 60 °C with overnight stirring at 300 rpm.
For the composite perovskite solution formation the prepared CsPbBr3 DMSO solution, ~1 mol molecular weight (MV) polyethylene oxide (PEO) (Sigma-Aldrich) DMSO solution (concentration 20 mg∙mL−1) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (anhydrous, 99.99% trace metals basis, Sigma-Aldrich) DMSO solution (concentration 10 mg∙mL−1) were mixed in 1∶0.1∶0.01 dry components wt. ratio, respectively, with subsequent overnight stirring at 60 °C and 300 rpm.
To prepare the prepatterned n++-Si(100) substrate for composite perovskite layer deposition, its surface was activated in 10 W O2 plasma (setup model low-cost Zepto, Diener Electronic) for 2 mins to improve wettability to perovskite solution. The composite film (resulting thickness ~ 140 nm, see
Transparent top contact formation
Our transparent top contact is based on pads of thin films of single-walled carbon nanotubes (SWCNTs). SWCNTs were produced with an aerosol (floating catalyst) chemical vapor deposition method and collected as a randomly oriented network on nitrocellulose filters (HAWP, Merck Millipore)
Device SEM imaging
To study the thickness and morphology of the inorganic perovskite layer scanning electron microscopy (SEM) was utilized. For the characterization, the sample was cut across the pixel area. The cross-section (CS) characterization was carried out using Zeiss Supra 25 SEM (accelerating voltage = 5 kV). The CS-SEM images of the structure are given in
Device characterization
The device’s J-V curves and J tracking curves were acquired with a Keithley 2401 source meter. Data on device electroluminescence and color coordinates were collected with Telescopic Optical Probe 150 of CAS 120 Instrument Systems spectroradiometer. The PeLEC device’s radiant power was measured with a Newport 1936-R power meter.
For photodetector behavior measurements, a continuous-wave (CW) laser diode of 450 nm wavelength with the maximum output optical power density of 405.85 mW/cm2 (maximum output optical power—6.38 mW; laser spot size 1.57 mm2) was used as an excitation source. The laser output optical power was controlled with an optical filter wheel FW212CNEB, (ThorLabs), that provides a range of illumination intensities. Maximal laser output optical power density equals to ~18 suns in equivalent (eqv.) to AM1,5G spectrum power density at ~450 nm or to ~4 suns in integral (int.) sun power density (also at AM1,5G). The detailed comparison of the experimental laser incident power densities to sun power density, which is important to get a picture on suitability of the device for applications in indoor and outdoor conditions, is shown in SI
Heat distribution imaging was acquired with a commercially available IR-imaging camera “Seek Thermal”. The two types of samples were compared in this measurement: our n++-Si(100)/CsPbBr3:PEO:LiTFSI/SWCNT structure and the standard soda-lime glass/ITO/CsPbBr3:PEO:LiTFSI/SWCNT structure, both placed on thermo-insulating surface for in-operation imaging. The ITO layer on the glass substrate was patterned by laser ablation (picosecond Nd:YVO4 laser, series PX100, SOLAR LS) into devices with active area equivalent to structures on n++-Si. All measurements were performed at ambient conditions.
Calculation
The numerical simulation of the dual-function n++-Si(100)/CsPbBr3 heterostructure was performed in the COMSOL Multiphysics package utilizing the drift-diffusion model in 1D geometry across Si/perovskite/SWCNT layers, at the axis normal to the silicon substrate surface. Non-ideality of interfaces of electrical contact layers and the properties of the composite perovskite/SWCNT interface were not taken into consideration. The CsPbBr3 material properties were taken from the literature
Results and discussion
Light-emitting electrochemical cell performance
The measured composite perovskite PeLEC electroluminescence spectra are shown in
Figure 3.Composite perovskite PeLEC key figures-of-merit. (
The external quantum efficiency of our device was calculated with the following equation:
where
In
Figure 4.(
To dynamically investigate the PeLEC performance, the current density and luminance tracking was performed at a constant applied bias of 3.7 V during 8 minutes, the data are shown in
Figure 5.(
All presented in this report device in-operation characterization was carried out during the first 72 h after fabrication. Our devices’ lifetime under operation at 2.6 V (luminance 300 cd/m2) was measured to be 4800 s (~1 h and 20 min) before inevitable active layer degradation (short-cut observed). Nevertheless, composite perovskite PeLECs demonstrate distinctive on-shelf stability—they retain their light-emitting properties (with the similar EL efficiency) over 1440 h (more than two months). We believe that PeLEC on-shelf lifetime significantly exceeds two months, although we did not check much further.
Technological potential demonstrations
To illustrate the applicability of our PeLEC devices, we designed and fabricated an indicator display frame, in a form of printed circuit board (PCB), for six samples, having total of 24 n++-Si(100)/CsPbBr3:PEO:LiTFSI/SWCNT pad pixels, with possibility to address every individual pixel separately using a separate addressing pixels PCB, see
Figure 6.The dual-function PeLEC devices indicator display images. (
We demonstrated not only the fully operational display based on our device, but also, we took a chance to creatively demonstrate the miniaturization potential of our PeLEC structures, see
Figure 7.Optical images of our n++-Si(100)/CsPbBr3:PEO:LiTFSI/SWCNT mat devices in shape of. (
Light-detecting performance
To evaluate light-detecting device performance, we measured devices J-V curves in dark and under laser illumination, as well as its external quantum efficiency (EQE) and responsivity (R).
The typical J-V curves for the device operating in the regime of photodetector are shown in
Figure 8.Composite perovskite photodiode key figures-of-merit. (
The photodetector EQE spectral study provides details on the system operation regime at negative applied bias, see
The device responsivity—a measure of photodetector’s sensitivity to light, expressed as
In
In
To further give necessary evaluation to our photodetector performance, an evaluation of key figures-of-merit were executed. We evaluated the linear dynamic range (LDR) of our photodetector. By definition, the device’s LDR illustrates the range of laser optical powers where the detected signal (photocurrent) is linearly proportional to the laser incident radiant power. The LDR is calculated as
Next, we looked at specific detectivity (D*)—a crucial photodetector figure-of-merit, that helps to assess the photodetectors signal-to-noise ratio – is normally approximates as
All in all, we conclude that even though the PeLEC demonstrates an impactful potential for light-detection, there are indisputable flaws in the architecture of our device. Further optimization of charge separation layers and electrode selectivity is required.
Heat distribution study
To evaluate in-operation temperature dissipation in our dual-function device on Si substrate compared to temperature dissipation in conventional soda-lime glass/ITO substrate structures infra-red (IR) imaging was utilized. The two identical in device area (active region thickness and material), transparent top contact processing, but different in the substrate material devices were prepared. One sample had n++-Si(100)/Al as its bottom contact, while another one had ITO/glass. The typical in-operation images of two types of devices are shown in Supplementary information
In our numerical calculations, the system on Si substrate emits 2.5 times more heat than the system on glass. The numerically simulated maps to compare two studied systems are given in Supplementary information
Conclusion
We have demonstrated the dual-function light-emitting/light-detecting perovskite device on a silicon substrate proving its high technological potential by not only fabrication of an indicator display with individual pixel addressing, but also, we have achieved high resolution with our miniaturized devices. Our light emitting device is a light-emitting electrochemical cell, which provides light electroluminescence efficiency of 1.3×105 lm/W and luminance more than 7000 cd/m2. In the light-detecting regime of operation, sensitivity of our device reaches 0.75 A/W with specific detectivity 8.56×1011 Jones and LDR 48 dB. We have successfully shown that silicon is a promising substrate for applications where devices are required to withstand high thermal heating (i.e. 40% lower thermal heating, when 32.7% higher electrical power is applied). Although, we admit there are optimization prospects to our technology as well, such as optical interface engineering between Si and perovskite layer (e.g. Al layer for “mirror”-like surface) and device electrical stability improvement via transport and/or passivation layers introduction (e.g. amorphous GaP or GaN layer would act as a hole-blocking layer).
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Maria Baeva, Dmitry Gets, Artem Polushkin, Aleksandr Vorobyov, Aleksandr Goltaev, Vladimir Neplokh, Alexey Mozharov, Dmitry V. Krasnikov, Albert G. Nasibulin, Ivan Mukhin, Sergey Makarov. ITO-free silicon-integrated perovskite electrochemical cell for light-emission and light-detection[J]. Opto-Electronic Advances, 2023, 6(9): 220154
Category: Research Articles
Received: Sep. 20, 2022
Accepted: Feb. 27, 2023
Published Online: Nov. 15, 2023
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