Large-area Devices Research Articles

Intralayer/Interlayer Codoping Stabilizes Polarity Modulation in 2D Semiconductors for Scalable Electronics.

2D semiconductors show promise as a competitive candidate for developing future integrated circuits due to their immunity to short-channel effects and high carrier mobility at atomic layer thicknesses. The inherent defects and Fermi level pinning effect lead to n-type transport characteristics in most 2D semiconductors, while unstable and unsustainable p-type doping by various strategies hinders their application in many areas, such as complementary metal-oxide-semiconductor (CMOS) devices. In this study, an intralayer/interlayer codoping strategy is introduced that stabilizes p-type doping in 2D semiconductors. By incorporating oppositely charged ions (F and Li) with the intralayer/interlayer of 2D semiconductors, remarkable p-type doping in WSe2 and MoTe2 with air stability up to 9 months is achieved. Notably, the hole mobility presents a 100-fold enhancement (0.7 to 92 cm2 V-1 s-1) with the codoping procedure. Structural and elemental characterizations, combined with theoretical calculations validate the codoping mechanism. Moreover, a CMOS inverter and more complex logic functions such as NOR and XNOR, as well as large-area device arrays are demonstrated to showcase its applications and scalability. These findings suggest that stable and straightforward intralayer/interlayer codoping strategy with charge-space synergy holds the key to unlocking the potential of 2D semiconductors in complex and scalable device applications.

Charged Impurity Scattering and Electron-Electron Interactions in Large-Area Hydrogen Intercalated Bilayer Graphene.

Intercalation is a promising technique to modify the structural and electronic properties of 2D materials on the wafer scale for future electronic device applications. Yet, few reports to date demonstrate 2D intercalation as a viable technique on this scale. Spurred by recent demonstrations of mm-scale sensors, we use hydrogen intercalated quasi-freestanding bilayer graphene (hQBG) grown on 6H-SiC(0001), to understand the electronic properties of a large-area (16 mm2) device. To do this, we first analyze Shubnikov-de Haas (SdH) oscillations and weak localization, permitting determination of the Fermi level, cyclotron effective mass, and quantum scattering time. Our transport results indicate that at low temperature, scattering in hQBG is dominated by charged impurities and electron-electron interactions. Using low- temperature scanning tunneling microscopy and spectroscopy (STS), we investigate the source of the charged impurities on the nm-scale via observation of Friedel oscillations. Comparison to theory suggests that the Friedel oscillations we observe are caused by hydrogen vacancies underneath the hQBG. Furthermore, STS measurements demonstrate that hydrogen vacancies in the hQBG have an extremely localized effect on the local density of states, such that the Fermi level of the hQBG is only affected directly above the location of the defect. Hence, we find that the calculated Fermi level from SdH oscillations on the millimeter scale agrees with the value measured locally on the nanometer scale with STS measurements.

Challenges and opportunities in high efficiency scalable and stable perovskite solar cells

Perovskite solar cells (PSCs) are the fastest-growing photovoltaic (PV) technology and hold great promise for the photovoltaic industry due to their low-cost fabrication and excellent efficiency. To achieve commercial readiness level, the most important factor would be yield beyond 95% at the PSC module levels. The current essential requirements for PSCs are reproducibility of high efficiency devices, scalability, and stability. The reported certified high efficiency (24–26%) results are based on the use of FAPbI3 perovskites with a bandgap of Eg≈ 1.5 eV, and the typical device's active area ranges from ≈ 0.1 cm2 to a maximum of 1 cm2. However, relatively higher bandgap PSCs are essential, especially in tandem solar cell applications. Hence, optimization of higher bandgap PSCs is a necessity. As the bandgap of the perovskites increases, the efficiency goes down due to reduced JSC and increased VOC loss. Therefore, understanding the loss mechanism and corresponding solutions need to be developed. Scaling up the device's active area without compromising the fill factor and, hence, efficiency is non-trivial. So, understanding the loss mechanism in large area devices is crucial. The stability analysis reported in the literature is inconsistent, preventing data comparison and identifying various degradation factors or failure mechanisms. Moreover, how the accelerated tests would be useful in predicting the real lifetime of the solar cells is yet to be developed. So, understanding the knowledge and the technological gaps between laboratory and industry-scale production is crucial for further development. Therefore, in this review article, we discuss the challenges and opportunities for scalable and stable high efficiency PSCs.

Methods for Studying the Electrical Characteristics of the Epitaxial Layers of n/p-InxGa1 – xAs Solid Solutions for Large-Area Device Structures

Methods for Studying the Electrical Characteristics of the Epitaxial Layers of n/p-InxGa1 – xAs Solid Solutions for Large-Area Device Structures

Spin-Coated and Vacuum-Processed Hole-Extracting Self-Assembled Multilayers with H-Aggregation for High-Performance Inverted Perovskite Solar Cells.

We report a highly crystalline self-assembled multilayer (SAMUL) that is fundamentally different from the conventional monolayer or disordered bilayer used for hole-extraction in inverted perovskite solar cells (PSCs). The SAMUL can be easily formed on ITO substrate to establish better surface coverage to enhance the performance and stability of PSCs. A detailed structure-property-performance relationship of molecules used for SAMUL is established through a systematic study of their crystallinity, molecular packing, and hole-transporting properties. These SAMULs are rationally optimized by varying their molecular structures and deposition methods through thermal evaporation or spin-coating for fabricating PSCs. The CbzNaphPPA-based SAMUL was chosen for fabricating inverted PSCs due to it exhibiting the highest crystallinity and hole mobility which is derived from the ordered H-aggregation. This resulted in a remarkably high fill factor of 86.45 %, which enables a very impressive power conversion efficiency (PCE) of 26.07 % to be achieved along with excellent device stability (94 % of its initial PCE retained after continuous operation for 1200 h under 1-sun irradiation at maximum power point at 65 °C). Additionally, a record-high PCE of 23.50 % could be achieved by adopting a thermally evaporated SAMUL. This greatly simplifies and broadens the scope for SAM to be used for large-area devices on diverse substrates.

Integration of highly sensitive large-area graphene-based biosensors in an automated sensing platform

Graphene-based biosensors, featuring exceptional electronic, mechanical, and surface properties, have emerged as frontrunners in advanced sensing technologies. However, to achieve widespread industrial adoption, advancements in the fabrication and integration of large-area graphene devices are essential. Critical parameters such as enhanced sensitivity, scalable production methods, economic viability, integration capabilities, and consistent uniformity must be meticulously addressed. In this work, we demonstrate that our ultra-clean, chemical wet transfer protocol of large-area graphene enables a scalable, smooth integration of graphene into an established assay platform for transporter protein drug discovery. Furthermore, we demonstrate sensitive detection of electrolytic buffers, varying pH, bovine serum albumin (BSA) and single-stranded DNA (ssDNA) adsorption, using our large-area graphene solution-gated field-effect transistor (SGFET) sensors, thereby proving their robust and reliable performance. The sensors’ biocompatibility and ion sensitivity, down to the picomolar range, substantiate their suitability for the investigation of electroactive transport in ion channels and membrane transporters.

Real-Time Radiation Beam Monitoring by Flexible Perovskite Thin Film Arrays.

Real-time and in-line transversal monitoring of ionizing radiation beams is a crucial task for several applications which span from medical treatments to particle accelerators in high energy physics. Here a flexible and large area device based on 2D hybrid perovskite thin films (phenylethylammonium lead bromide), fabricated onto a thin flexible polyimide substrate, able to map the transversal beam profile of high energy radiation beams is reported. The performance of this novel tool is here compared with the one offered by standard commercial large-area technology, namely radiochromic sheets. The great potential of this class of devices is demonstrated by successfully mapping in real-time a 5 MeV proton beam at fluxes between 108 and 1010 H+ s-1 cm-2, confirming the capability to operate in a radiation-harsh environment without output signal saturation issues. The versatility and scalability of here proposed detecting system are demonstrated by the development of a multipixel array able to map in real-time a 40 kVp X-ray beam spot (dose rate 8 mGy s-1). Perovskite thin film-based detectors are thus assessed as a very promising class of thin, flexible devices for real-time, in-line, large-area, conformable, reusable, transparent, and low-cost transversal beam monitoring of different ionizing radiation.

Solution-processed ZnO quantum dot thin films with low solvent residues and ultra-flat surfaces

ZnO quantum dots are considered a desirable material for the electron transport layer (ETL) in thin-film optoelectronic devices, determining their efficiency and stability. Solution-processed ZnO quantum dot films are fascinating due to the potential for low-cost manufacture of large-area devices and the compatibility with flexible substrates. However, eliminating solvent residues from solution-derived ZnO films remains a challenge, as their presence can significantly impact the efficiency and performance of the devices. Herein, we reported a straightforward and controllable strategy to overcome the above problem, aiming to achieve low solvent residues and ultra-flat ZnO films. Methanol, with its low boiling point and high relative evaporation rate, is utilized as a dispersing solvent for ZnO quantum dots, the resulting thin films exhibit low solvent residue, as confirmed by TGA and NMR analyses. Moreover, we achieved a stable monodisperse state of ZnO quantum dots in methanol solvent for three months by a simple temperature control method. The ZnO film prepared using a low-temperature spin-coating technique demonstrates extremely low surface roughness (RMS less than 1 nm).

Experimental qualification and modelling of the non-linear response of the DEPFET active pixel sensor for the DSSC camera

A modified Depleted P-Channel Field Effect Transistor (DEPFET) is the key feature of the DEPFET Sensor with Signal Compression (DSSC), a 1 Mpixel X-ray camera aiming at ultra-fast imaging of soft X-rays at the European XFEL. Operation of large-area devices with a large number of DSSC-type DEPFET pixels requires the accurate knowledge of the sensitivity of the response to the relevant DEPFET parameters. The paper presents the experimental qualification of the response of DSSC-type DEPFET pixels in the space of 4 relevant parameters: drain current, source voltage, drain voltage and back side voltage. The obtained results allow estimation of the impact of the inevitable parameter fluctuations in large monolithic sensors and of the actual trimming range of the shape of signal compression in view of the pixelwise calibration of the 1 Mpixel DSSC camera.

High brightness terahertz quantum cascade laser with near-diffraction-limited Gaussian beam

High-power terahertz (THz) quantum cascade laser, as an emerging THz solid-state radiation source, is attracting attention for numerous applications including medicine, sensing, and communication. However, due to the sub-wavelength confinement of the waveguide structure, direct beam brightness upscaling with device area remains elusive due to several mode competition and external optical lens is normally used to enhance the THz beam brightness. Here, we propose a metallic THz photonic crystal resonator with a phase-engineered design for single mode surface emission over a broad area. The quantum cascade surface-emitting laser is capable of delivering an output peak power over 185 mW with a narrow beam divergence of 4.4° × 4.4° at 3.88 THz. A high beam brightness of 1.6 × 107 W sr−1m−2 with near-diffraction-limited M2 factors of 1.4 in both vertical and lateral directions is achieved from a large device area of 1.6 × 1.6 mm2 without using any optical lenses. The adjustable phase shift between the lattices enables a stable and high-intensity surface emission over a broad device area, which makes it an ideal light extractor for large-scale THz emitters. Our research paves the way to high brightness solid-state THz lasers and facilitates new applications in standoff THz imaging, detection, and diagnosis.

High Current Efficiency Red Perovskite Light-Emitting Diodes Meeting Rec. 2020 Standard.

Cesium lead iodide light-emitting diodes (LEDs) are attractive for displays due to their Rec. 2020 red standard compliance. However, achieving high current efficiencies (CEs), which is important for displays, is challenging because their emission spectrum is near the tail of the photopic luminosity function. Substituting some iodine with bromine can improve CEs by enlarging the bandgap, but defects easily form in iodine-bromine mixed perovskites. Here, we successfully reduced defect formation by adding organic ammonium salts and zwitterions. The organic ammonium salts do not form low-dimensional perovskites under the hydrogen bonding interaction of zwitterions. Instead, they passivate the cesium vacancy by forming new hydrogen bonds after perovskite crystallization. This approach leads to a red perovskite LED with a high CE of 12.8 cd A-1 and a peak external quantum efficiency of 20.3%, meeting the Rec. 2020 standard. It can be extended to large-area devices (2500 mm2) without a significant efficiency loss.

(Invited) Development of Novel Wavelength-Selective Organic Semiconductors for Agrivoltaics and Transparent Phototransistors

Development of organic semiconductors based on pi-conjugated systems for use in solar cells, field-effect transistors, light-emitting diodes, and phototransistors has become an active area of research because of the potential applicability of these materials to large-area, lightweight, and flexible devices. Another advantage of such organic materials is the ease of tuning the molecular properties, which can be realized by versatile molecular design in organic chemistry. In this contribution, we will focus on the development of green-light or near-infrared wavelength-selective organic semiconductors, which can be applied to agrivoltaics and organic phototransistors, respectively.

Towards Large-Area Black Phosphorous Midwave-IR Optoelectronics

High-efficiency mid-wavelength infrared (mid-IR, 3–5 µm) optoelectronics, including light emitting diodes (LEDs) and photodetectors, are of high demand for emerging applications in spectroscopy, imaging, and gas sensing. Black phosphorus (bP) has emerged as a unique optoelectronic material for mid-IR applications with performances surpassing those of conventional III-V and II-VI semiconductors of similar bandgap. In this talk, I will present recent advancements on understanding and controlling the radiative and non-radiative recombination rates as a function of bP thickness. We observe higher photoluminescence quantum yields in bP as compared to conventional III-V and II-VI semiconductors of similar bandgaps due to the smaller Auger recombination rate. As a result, bP mid-IR LEDs with external quantum efficiency of >4% are reported, outperforming the state-of-the-art in this wavelength range. Furthermore, device encapsulation and packaging technologies are explored with extrapolated half lifetime of ~15,000 hours based on accelerated lifetime measurements. Finally, I will present strategies for large-area device fabrication and processing.

(Invited) Silicon Nanocrystals and Electrum Nanoclusters with High Quantum Yield for Light Converting Applications

While QDs are typically made of semiconductors, metals at low dimensions also turn to discrete electronic structure. The characteristic transition size from bulk to nanodot is lower, because Fermi level position is at the band middle, while discretization of levels starts from the band edge. Therefore, only for sizes of a metal entity ~ 1 nm a QD-like behavior manifests.Here we show that metal nanoclusters Au16Ag7 of an electrum alloy (gold-silver) with adamantanethiolate ligands possess PL quantum yield of ~ 70% in a thiol-ene polymer matrix [1]. PL is in NIR range with a large Stokes shift. Due to parity-forbidden transition the PL lifetime is in microseconds. These characteristics are similar to silicon QDs, where optical transition is also partly forbidden. Luminescence from Si QDs (5-10 nm size) may also feature high quantum efficiency when a defect-free core with good surface passivation is prepared. We have demonstrated a new synthesis method, which can reduce precursor cost by an order of magnitude from the established HSQ-based technique [2]. Si QDs prepared in this way have near-unity internal and > 50% external (quantum yield) efficiency with a large Stokes shift. In both nanomaterials the re-absorption is suppressed, which is of value for several applications.One such application is a semi-transparent photovoltaics for glazing in building-integration. It is based on a luminescent solar concentrator concept, where high efficiency and a large Stokes shift are necessary requirements for nanophosphors. In this configuration absorbed solar light is re-emitted and a large fraction of it is guided by total internal reflection to the edges for collection by standard solar cells. As a proof-of-concept we fabricated 20x20 cm2 prototypes, where Si QD-doped polymer layer is sandwiched between glass plates in a triplex geometry. Such “solar windows” feature high transparency (>80%), low haze (<3%), high color rendering index (~ 88) and, at the same time, deliver up to 0.6 W of electrical peak power under one sun [3]. Original measurement techniques were developed to characterize large-area devices [4,5].

Large-area superconducting nanowire arrays fabricated by nano laser direct writing

We report on the fabrication, structural, and electrical transport characterizations of superconducting nanowire arrays based on nano-laser direct writing (NLDW). The thermal excitation-induced micro/nano fabrication based on the interactions between NLDW and superconducting Nb films was experimentally analyzed and simulated. Experimentally, the arrays of superconducting nanowires have an area of 190 × 190 μm2 with a critical transition temperature Tc of 7.8 K and a critical current density Jc of 20.8 MA cm−2 at 4.0 K. The width and arrangement of the nanowires are precisely controlled, exhibiting a minimal loss of 0.6 K in Tc and excellent Jc after LDW. The width of superconducting nanowires could be further optimized by adjusting parameters such as laser power, irradiation gap, and delay of points. Compared with electron beam lithography and focused ion beam, to some extent, the nanowires fabrication process based on NLDW provides a more efficient and cost-effective path for fabricating large-area superconducting circuits and devices.

Alpha particle detection based on low leakage and high-barrier vertical PtOx/β-Ga2O3 Schottky barrier diode

High-performance radiation detectors are essential in many sectors spanning medical diagnostics, nuclear control, and particle physics. Ultrawide bandgap semiconductor materials have become one of the most promising candidates due to their excellent performance. Here, based on β-Ga2O3, a Schottky diode-type alpha particle detector was demonstrated. In order to reduce the reverse leakage current of the large-area device, the metal-oxide electrode PtOx was introduced to form high-barrier contacts (1.83 eV) with Ga2O3. The device exhibits a low leakage current density of 63 pA/cm2 at −100 V and apparent energy spectra of 241Am generated alpha particles with an energy of 5.486 MeV at various reverse voltages from −40 to −120 V. The charge collection efficiency (CCE) and energy resolution of the device (at −120 V) are 31.7% and 15.3%, respectively. Meanwhile, the mechanism of interaction between alpha particles and β-Ga2O3 was analyzed, and a 45° oblique incidence was adopted to increase the deposited energy of alpha particles in the depletion region. Furthermore, the differences between actual CCE and theoretical CCE are investigated as guidance for further improving detector performance. This work reveals the great potential and good prospects of Ga2O3 as an economical, efficient, and radiation-resistant ionizing radiation detector.

Electrochromic windows with fast response and wide dynamic range for visible-light modulation without traditional electrodes

Electrochromic (EC) devices represent an emerging energy-saving technology, exhibiting the capability to dynamically modulate light and heat transmittance. Despite their promising potential, the commercialization of EC devices faces substantial impediments such as high cost, intricate fabrication process, and low optical contrast inherent in conventional EC materials relying on the ion insertion/extraction mechanism. In this study, we introduce an innovative “electrode-free” electrochromic (EC) device, termed the EECD, which lacks an EC-layer on the electrodes during device assembling and in the bleached state. This device features a simplified fabrication process and delivers superior optical modulation. It achieves a high optical contrast ranging from 68-85% across the visible spectrum and boasts a rapid response time, reaching 90% coloring in just 17 seconds. In addition, EECD exhibits stable cycling for over 10,000 cycles without noticeable degradation and maintains functionality across a broad temperature range (0 °C to 50 °C). Furthermore, the fabricated large-area devices (40 cm × 40 cm) demonstrate excellent tinting uniformity, suggesting excellent scalability of this approach. Our study establishes a paradigmatic breakthrough for EC smart windows.

Introducing steric groups to thermally activated delayed fluorescence emitter for constructing efficient non-doped solution-processed organic light-emitting diodes

Solution-processed organic light-emitting diodes (OLEDs) remain a reliable approach towards large-area and flexible display devices, but also hold higher requirement on luminescent materials. It is still challenge to develop emitting layers with great solution-processable property and excellent luminous behavior, and especially difficult for non-doped emitting materials. In this work, a TADF emitter, namely 2,3,5,6-tetrakis(4-([1,1':3′,1″-terphenyl]-5′-yl)-9H-carbazol-9-yl)benzonitrile (3Ph-4CzBN), was designed and synthesized by introducing the steric-hindrance triphenyl unit to 2,3,5,6-tetrakis(carbazol-9-yl) benzonitrile (4CzBN) which is usually applied to vacuum evaporation. The incorporation of triphenyl groups significantly increased the molecule weight, thereby rendering 3Ph-4CzBN suitable for solution-processed OLEDs. Meanwhile, 3Ph-4CzBN exhibited two-fold of photoluminescence quantum yield values in pure film than 4CzBN, indicating fluorescence quenching was relatively suppressed by steric groups. The solution-processed OLEDs employed 3Ph-4CzBN as non-doped emitting layer, achieved a maximum external quantum efficiency of 12.8 %, as well as current efficiency and power efficiency up to 34.2 cd A−1 and 23.9 lm W−1, respectively.

Two-dimensional perovskitoids enhance stability in perovskite solar cells.

Two-dimensional (2D) and three-dimensional (3D) perovskite heterostructures have played a key role in advancing the performance of perovskite solar cells1,2. However, the migration of cations between 2D and 3D layers results in the disruption of octahedral networks, leading to degradation in performance over time3,4. We hypothesized that perovskitoids, with robust organic-inorganic networks enabled by edge- and face-sharing, could impede ion migration. We explored a set of perovskitoids of varying dimensionality and found that cation migration within perovskitoid-perovskite heterostructures was suppressed compared with the 2D-3D perovskite case. Increasing the dimensionality of perovskitoids improves charge transport when they are interfaced with 3D perovskite surfaces-this is the result of enhanced octahedral connectivity and out-of-plane orientation. The 2D perovskitoid (A6BfP)8Pb7I22 (A6BfP: N-aminohexyl-benz[f]-phthalimide) provides efficient passivation of perovskite surfaces and enables uniform large-area perovskite films. Devices based on perovskitoid-perovskite heterostructures achieve a certified quasi-steady-state power conversion efficiency of 24.6% for centimetre-area perovskite solar cells. We removed the fragile hole transport layers and showed stable operation of the underlying perovskitoid-perovskite heterostructure at 85 °C for 1,250 h for encapsulated large-area devices in ambientair.

Polyaniline microspheres using potassium polyvinyl sulfate as template for large-area broadband electrochromic device with large infrared emissivity variation

In the development of polyaniline (PANI) based large-area broadband electrochromic devices, we employed a controlled deposition process using potassium polyvinyl sulfate (PVSK) as a template to regulate the morphology of PANI. This resulted in consistent spherical particle morphology and heightened electrochemical activity in PVSK-PANI films. The simple structure of PVSK, coupled with its similar IR absorption to polyethylene and sulfuric acid, mitigated any detrimental effects on the broadband electrochromic properties. In small-area (2 × 2 cm²) PVSK-PANI electrochromic devices, we observed maximum emissivity changes of 0.47, 0.51, and 0.49 in the 3-5 μm, 8-14 μm, and 2.5-15 μm ranges, respectively. Expanding our approach to large-area devices (20 × 20 cm2), we achieved even more promising results. The PVSK-PANI based electrochromic devices achieved maximum emissivity changes of 0.55, 0.46, and 0.46 within the same spectral ranges of 3-5 μm, 8-14 μm, and 2.5-15 μm, respectively. Notably, these large-area electrochromic devices demonstrated a remarkable capacity to modulate infrared temperature by up to 10.4 °C at a background temperature of 70 °C.