Deep Level Defects Research Articles

Defect-Engineering-Induced Vacancy-Rich Bi2S3-x@AuNPs with Enhanced Photothermal Activity for Sensitive Bimodal-Type Gentamicin Monitoring.

One of the most promising approaches to effectively modulate the performance of immunochromatography (ICA) is the rational design of nanomaterials. It is anticipated to facilitate highly sensitive ICA analysis by introducing and controlling the internal defect structures of nanomaterials. Herein, we designed Bi2S3-x@AuNPs with deep-level defect properties, revealing that these deep defects act as electron-hole nonradiative complex centers to promote phonon production, ultimately leading to photothermal analytical performance in ICA. By effectively regulating the defect density, the assay showed extraordinary colorimetric intensity, photothermal performance, and stability, which were conducive to constructing sensitive ICA. With a proof-of-concept for gentamicin (Gen), the limit of detection (LOD) was determined to be 0.0358 ng mL-1, with overall recoveries ranging from 84.40% to 108.30% in both milk and milk powder samples. It demonstrates the importance of the rational design of internal defect structures to improve analytical performance and broaden the application of ICA.

Unveiling the Monoclinic Phase in CsPbBr3-xClx Perovskite Crystals, Phase Transition Suppression and High Energy Resolution γ-Ray Detection.

All-inorganic CsPbBr3 and CsPbCl3 perovskites are promising materials for high-performance solar cells and advanced radiation detection technologies with high stability. Here we report that CsPbBr3-xClx (x = 0-3) crystals exhibit eutectoid behavior for the melting points and phase transition temperatures. The well-known halide perovskite cubic phase transition temperature shifts near room temperature (∼37 °C for CsPbBr2Cl). We conducted an extensive crystallographic analysis on single crystals of 7 different compositions, including the end members CsPbBr3 and CsPbCl3. Contrary to previous beliefs, we discovered they exhibit a monoclinic structure with space group symmetry P21/m at room temperature, rather than the orthorhombic Pnma. This new structural model is more precise and features a unit cell volume that is four times larger than that of the orthorhombic model. From high-quality single crystals of CsPbBr2Cl, grown by the Bridgman method, we constructed γ-ray detectors achieving an energy resolution of 7.2% at 200 V for 57Co radiation. Thermally stimulated current spectroscopy of the CsPbBr2Cl samples revealed that the defect densities in crystals from different regions of the ingot were relatively uniform, with values of ∼4.72 × 1012 and ∼5.09 × 1012 cm-3. These findings indicate that low deep-level defect densities can be achieved that are consistent with the notable performance of the CsPbBr2Cl perovskite as a high-energy γ radiation detector.

Deep level defect passivation for printable mesoporous CsSnI3 perovskite solar cells with efficiency above 10%

The lead-free inorganic perovskite CsSnI3 is considered as one of the best candidates for emerging photovoltaics. Nevertheless, CsSnI3-based perovskite solar cells experience a significant drop in performance due to the nonradiative recombination facilitated by trapping. Here, we show an electron donor passivation method to regulate deep-level defects for CsSnI3 perovskite with electron donor pyrrole. Experimental observations combined with theoretical simulations verify that the saturation of Tin dangling bonds with pyrrole on the CsSnI3 surface via a Lewis acid-base addition reaction can significantly reduce the density of deep-level defects. Consequently, the printable mesoporous perovskite solar cells with an FTO/compact-TiO2/mesoporous-TiO2/Al2O3/NiO/carbon framework device structure penetrated with CsSnI3 achieve a power conversion efficiency of up to 10.11%. To our knowledge, this represents the highest efficiency reported to date for lead-free perovskite-based printable mesoporous solar cells. Furthermore, the unencapsulated devices demonstrated remarkable long-term stability, retaining 92% of their initial efficiency even after 2400 h of aging in a nitrogen atmosphere.

Study of the effect of CdCl2 introduction on the high temperature activation treatment of CdTe:As polycrystalline thin films

V-doped CdTe polycrystalline films can achieve both doping activation and defect passivation by high-temperature CdCl2 heat treatment, but this requires simultaneous modulation of the amount of CdCl2 introduced to obtain high-quality films. It is found that increasing the CdCl2 introduction does not change the physical phase structure and lattice constant of CdTe:As thin films, but promotes grain recrystallisation, and can promote the formation of A-center, and inhibit the formation of Cd vacancy (VCd) defects, as well as the formation of deep energy level defects. The results provide guidance for the improvement of high-temperature CdCl2 heat treatment of V-doped CdTe polycrystalline thin films.

Suppressing Se Vacancies in Sb2Se3 Photocathode by In Situ Annealing with Moderate Se Vapor Pressure for Efficient Photoelectrochemical Water Splitting.

Sb2Se3 emerges as a promising material for solar energy conversion devices. Unfortunately, the common deep-level defect VSe (selenium vacancy) in Sb2Se3 results in a low solar conversion efficiency. The post selenization process has been widely adopted for suppressing VSe. However, the effect of selenization on suppressing VSe is often compromised and even more VSe are induced due to defect-correlation. Herein, high-quality Sb2Se3 films are prepared using an unconventional selenization process, with precisely regulating in situ annealing Se vapor pressure. It is found that moderate Se vapor pressure annealing can efficiently suppress VSe by overcoming defect-correlation, as well as promotes grain growth and forms a better heterojunction band alignment. Consequently, the Sb2Se3 photocathode shows a high-level photocurrent of 19.5 mA cm-2 at 0 VRHE, an onset potential of 0.40 VRHE and a half-cell solar-to-hydrogen conversion efficiency of 1.9%, owing to the inhibited charge recombination, excellent charge transport and interface charge extraction. This work provides a significant insight to suppress deep-level defect VSe by adjusting Se vapor pressure for efficient Sb2Se3 photocathode.

Oxidative Passivation of FAPbI3 via Femtosecond Laser for Enhanced Photoluminescence and Photoresponse Performance

AbstractThe presence of uncoordinated Pb atoms in perovskite materials, acting as non‐radiative recombination centers, significantly degrades the performance of perovskite‐based photoelectronic devices. Addressing this issue by passivating these deep energy level defects is essential for enhancing device performance. By now, the passivation methods are largely proposed by chemical additive engineering methods, which involve the oxidation of Pb through chemical additives. However, chemical passivation methods are often plagued by issues such as prolonged processing times, uncontrollable passivation regions uncontrollable, and environmental contamination. Here, a novel femtosecond laser oxidative passivation (FsLOP) technique for FAPbI3 is proposed, evidenced by X‐ray photoelectron spectroscopy (XPS) revealing the formation of Pb─O bonds. The role of peroxide anions in oxidation passivation is highlighted as pivotal. The oxidative passivation effect is further corroborated by a four‐fold increase in photoluminescence (PL) intensity and an exceptional improvement in photoresponse performance, achieving a detectivity of 6.77 × 1012 Jones. This work provides a deeper insight into the interaction between femtosecond lasers and perovskite materials, proposing an efficient, precisely controlled, and environmentally friendly way to improve the performance of perovskite photoelectronic devices.

Controlling the luminescence of CdSe quantum dots in the fluorinephosphate glass

A series of fluorophosphate glasses with CdSe and CdSe+ZnSe are successfully synthesized. After heat treatment above the glass transition temperature, CdSe quantum dots with sizes 1.5–5.5 nm are formed. The luminescence spectra of CdSe quantum dots are analyzed at various temperatures, excitation energies and chemical composition of glass. The influence of selenium content on the growth features of quantum dots is shown. The size dependence of luminescence quantum yield on the QDs size is found. The 2.0–2.5 nm-sized QDs demonstrate trap emission in the region of 1.7–1.85 eV with a maximum quantum yield of 60 %. It is found that only a broad band due to the transition from the low state of the conduction band and the shallow donor trap states to the deep accepter trap levels is observed. This broad emission band is observed at any selenium cadmium ratio and zinc introduction.

An ab-initio investigation of Sc and Y doped chalcopyrite MgGeN[formula omitted]

The doping of Scandium and Yttrium within chalcopyrite MgGeN2 were computationally investigated using density function theory (DFT) calculations. By calculating the formation energy, it was shown that independent single Sc and Y dopants energetically favor the occupation of the Mg site, inducing a shallow level within the conduction band. However, in the presence of a substitutional defect, the second dopant will occupy the neighboring Ge site. There is strong attractive interaction between two dopants, so that they are easily combined into a composite defect. In this case a shallow defect level appears above the valence band edge. Similar behavior is observed for the composite defects containing one dopant and an intrinsic cation vacancy, while those with one dopant and a nitrogen vacancy induce a deep defect level and greatly reduce the band gap. The investigation deepens the knowledge of Sc and Y doped II-IV-V2 compounds and may hence lead to more implementations.

Innovative In Situ Passivation Strategy for High-Efficiency Sb2(S,Se)3 Solar Cells.

An effective defect passivation strategy is crucial for enhancing the performance of antimony selenosulfide (Sb2(S,Se)3) solar cells, as it significantly influences charge transport and extraction efficiency. Herein, a convenient and novel in situ passivation (ISP) technique is successfully introduced to enhance the performance of Sb2(S,Se)3 solar cells, achieving a champion efficiency of 10.81%, which is among the highest recorded for Sb2(S,Se)3 solar cells to date. The first principles calculations and the experimental data reveal that incorporating sodium selenosulfate in the ISP strategy effectively functions as an in situ selenization, effectively passivating deep-level cation antisite SbSe defect within the Sb2(S,Se)3 films and significantly suppressing non-radiative recombination in the devices. Space-charge-limited current (SCLC), photoluminescence (PL), and transient absorption spectroscopy (TAS) measurements verify the high quality of the passivated films, showing fewer traps and defects. Moreover, the ISP strategy improved the overall quality of the Sb2(S,Se)3 films, and fine-tuned the energy levels, thereby facilitating enhanced carrier transport. This study thus provides a straightforward and effective method for passivating deep-level defects in Sb2(S,Se)3 solar cells.

Characterization Study of Deep-Level Defect Spatial Distribution, Emission Mechanisms, and Structural Identification

Abstract The characterization of defects in semiconductor materials and devices is crucial for enhancing the performance and reliability of semiconductor products. This tutorial review focuses on Deep Level Transient Spectroscopy (DLTS) as the primary analytical tool, thoroughly discussing its distinct advantages in deep-level defect characterization. However, it is unable to reveal the concentration-depth distribution of deep-level defects, neglects the dependency of carrier emission rates on the electric field, and fails to accurately identify defect structures.
To overcome these limitations, two enhanced DLTS techniques have been developed to extend the capabilities of DLTS. These enhancements include the utilization of graded fill pulse technology to accurately map defect distributions at various depths within devices, facilitating individual defect characterization across different layers of multilayered structures; the application of varying electric field strengths to samples to delve into the intricate physical mechanisms of defects during carrier emission processes; and the adjustment of the duration of electric pulse injection to monitor signal growth trends, deducing the microstructure of defects. The paper integrates research findings from a wide array of field experts, meticulously outlines a description of how to obtain the depth distribution of defect concentration in devices, furnishes quantitative criteria for both the Poole-Frenkel effect and phonon-assisted tunneling mechanisms of carrier emission, and provides specific examples for distinguishing between interface states/bulk defects and point defects/extended defects. This enhances both the theoretical and practical knowledge in this field. The advanced DLTS techniques outlined provide crucial guidance for defect characterization and performance optimization in semiconductor devices with new structures and materials.

In-situ construction of novel Sb2(S,Se)3/CdSe S-scheme heterojunction with enhanced photoelectrochemical performance

Abstract Antimony selenosulfide (Sb2(S,Se)3) was considered to have great potential for photoelectrochemical (PEC) water splitting applications due to its excellent chemical stability, good light absorption, abundant reserves and non-toxicity. However, Sb2(S,Se)3 faces some limitations in the field of PEC, such as the serious recombination problem of photogenerated carriers. Therefore effectively restraining its deep-level defects is the crucial for enhancing its photoelectrochemical properties. In this paper, We successfully fabricated Sb2(S,Se)3/CdSe S-scheme heterojunction via one-step hydrothermal method, which improves its solar absorption capacity, facilitates efficient carrier separation. And, Sb2(S,Se)3/CdSe S-scheme heterojunction can suppress the adverse effects of deep-level defects on the PEC performance of Sb2(S,Se)3. Under simulated solar irradiation, the light current density can reach 4.02 mA cm2 (33.5 times that of monomeric Sb2(S,Se)3) at 1.23 VRHE, accompanied by low initial voltage and extremely high surface charge injection efficiency. This study is of great significance for the application of Sb2(S,Se)3 in the PEC field.

Pushing the Limits of Photoconductivity via Hot Electrons in Deep Trap States in Plasmonic Architectures.

Although extensive research on the mechanisms of photoconductivity enhancement in plasmonic Schottky structures has been conducted, the photoconductive interplay between hot electrons and trapping states remains elusive. In this study, we explored the photoconductive relationship between plasmonic hot-carriers and defect sites present in plasmonic architectures consisting of N-face n-GaN and Au nanoprisms. Our experimental results clearly verified that the plasmonic hot-electrons generated by interband transitions preferentially occupied deep trap levels in n-GaN, thereby considerably enhancing the photoconductivity through the combination of photogating and photovoltaic effects. Our quantitative evaluation demonstrated that a mere 63% increase in hot-electron trapping leads to a 1.7-fold increased photocurrent under localized surface plasmon resonance (LSPR) excitation compared to the figure of photocurrent under non-LSPR stimulus. Our findings provide novel insights into the mechanisms of photoconductive enhancement for advanced plasmonic applications.

Analysis of deep level defects in nitrogen post-deposition annealed Ga2O3/SiC hetero-structured Schottky diodes grown by mist-CVD

Analysis of deep level defects in nitrogen post-deposition annealed Ga2O3/SiC hetero-structured Schottky diodes grown by mist-CVD

Additive engineering for efficient wide-bandgap perovskite solar cells with low open-circuit voltage losses.

High-performance wide-bandgap (WBG) perovskite solar cells are used as top cells in perovskite/silicon or perovskite/perovskite tandem solar cells, which possess the potential to overcome the Shockley-Queisser limitation of single-junction perovskite solar cells (PSCs). However, WBG perovskites still suffer from severe nonradiative recombination and large open-circuit voltage (Voc) losses, which restrict the improvement of PSC performance. Herein, we introduce 3,3'-diethyl-oxacarbo-cyanine iodide (DiOC2(3)) and multifunctional groups (C=N, C=C, C-O-C, C-N) into perovskite precursor solutions to simultaneously passivate deep level defects and reduce recombination centers. The multifunctional groups in DiOC2(3) coordinate with free Pb2+ at symmetric sites, passivating Pb vacancy defects, effectively suppressing nonradiative recombination, and maintaining considerable stability. The results reveal that the power conversion efficiency (PCE) of the 1.68eV WBG perovskite solar cell with an inverted structure increases from 18.51% to 21.50%, and the Voc loss is only 0.487V. The unpackaged device maintains 95% of its initial PCE after 500h, in an N2 environment at 25°C.

Amphipathic Astaxanthin Additive for Low Voltage-loss Perovskite Solar Cells With Enhanced Quasi-Fermi Level Splitting and Solar Hydrogen Production Application.

Even though the power conversion efficiency (PCE) of perovskite solar cells (PSCs) is nearly approaching the Schottky-Queisser limit, low open-circuit voltage (Voc) and severe Voc loss problems continue to impede the improvement of PCEs. Astaxanthin (ASTA) additive is introduced in the formamidinium lead triiodide (FAPbI3)perovskite film as an additive, which can facilitate the transportation of charge carriers and interact with Pb2+ by its distinctive groupings. Furthermore, the addition of ASTA decreases the defect's active energy, regulates the deep-level defect by filling up the grain boundaries (GBs), and promotes the crystallization of perovskite film. Remarkably, an enhanced quasi-Fermi level splitting (QFLS) of 1.164eV and a reduced Voc loss of only 96mV are realized. The champion PCE of 24.56% is attained by ASTA-modified PSCs on the basis of 22.75% PCE. Moreover, the PSCs that underwent ASTA modification demonstrate improved operational stability, ensuring consistent output in real-world scenarios. Furthermore, PSCs with an active area of 1 cm2 are used for water electrolysis to produce hydrogen and exhibit a PCE of 22.41%. This work offers an environmentally benign solution to address the inherent issues of FAPbI3 PSCs and lays the groundwork for the development of a prospective solar hydrogen production application.

Achieving 11.23 % efficiency in CZTSSe solar cells via defect control and interface contact optimization

The high open-circuit voltage deficit (VOC, def) caused by structural imperfections in the absorber layer and charge loss during carrier transport is a critical barrier affecting the performance of Cu2ZnSn(S,Se)4 (CZTSSe) devices. In this work, Ag was added to the DMF-based Cu+-Sn4+ system, which significantly improved the crystal morphology and electrical properties of the absorber layer. Additionally, optimizing the selenization process not only reduced surface roughness and eliminated voids at the bottom of the absorber layer but also resulted in the formation of a MoSe2 back interface layer with a more suitable thickness. These measures collectively enhanced the overall quality of the absorber layer, reducing the formation of deep-level defect clusters and effectively boosting carrier transport efficiency. Consequently, the concentration of bulk and interfacial defects decreased, and the impact of potential barriers on carrier movement was minimized. With these comprehensive improvements, the power conversion efficiency of CZTSSe solar cells increased from 8.48 % to 11.23 %. Our research demonstrates that optimizing the structure of the absorber layer can effectively enhance the performance of CZTSSe solar cells, providing valuable insights for the fabrication of high-efficiency devices in the future.

Elucidating the Role of Alkali Metal Carbonates in Impact on Oxygen Vacancies for Efficient and Stable Perovskite Solar Cells.

Effectively suppressing nonradiative recombination at the SnO2/perovskite interface is imperative for perovskite solar cells. Although the capabilities of alkali salts at the SnO2/perovskite interface have been acknowledged, the effects and optimal selection of alkali metal cations remain poorly understood. Herein, a novel approach for obtaining the optimal alkali metal cation (A-cation) at the interface is investigated by comparatively analyzing different alkali carbonates (A2CO3; Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3). Theoretical calculations demonstrate that A2CO3 coordinates with undercoordinated Sn and O on the surface, effectively mitigating oxygen vacancy (VO) defects with increasing A-cation size, whereas Cs2CO3 exhibits diminished preferability owing to enhanced steric hindrance. The experimental results highlight the crucial role of Rb2CO3 in actively passivating VO defects, forming a robust bond with SnO2, and facilitating Rb+ diffusion into the perovskite layer, thereby enhancing charge extraction, alleviating deep-level trap states and structural distortion in the perovskite film, and significantly suppressing nonradiative recombination. X-ray absorption spectroscopy analyses further reveal the effect of Rb2CO3 on the local structure of the perovskite film. Consequently, a Rb2CO3-treated device with aperture area of 0.14 cm2 achieves a notable efficiency of 22.10%, showing improved stability compared to the 20.11% achieved for the control device.

Over 10% efficient Cu2ZnSn(S, Se)4 Thin-Film cells prepared by aluminium doping

Cu2ZnSn(S,Se)4(CZTSSe) solar cell is of excellent development tendency because of lower pollution and outstanding power conversion efficiency(PCE). Yet, current PCE of CZTSSe is limited because of a high open-circuit voltage deficit, primarily put down to severe band tailing and carrier recombination. In this paper, absorber films were obtained by solution method and the influences of different aluminum doping concentrations on the properties of CZTSSe thin film cell were studied. Analysis about X-ray diffraction (XRD) and Raman spectroscopy confirms which Al has incorporated into CZTSSe thin film lattice and replaced Sn. Hall effect measurements reveal the improvement of carrier concentration on thin film absorber layer attribute to the formation of AlSn acceptor defects. Furthermore, X-ray photoelectron spectroscopy (XPS) reveals that Al enter into the CZTSSe lattice and Al is in the appropriate state of + 3 valence without generating additional harmful defects. More important, the generation of deep energy level defects and defect clusters associated with Sn were suppressed by replacing Sn with Al. Finally, the photovoltaic performance of different Al doped CZTSSe cells were characterized by conducting J-V and external quantum efficiency (EQE) tests. Remarkably, the CZTSSe solar cell with PCE as high as 10.59 % is obtained under a doping level of 6 % Al, which has an open circuit voltage of 522 mv. Compared with reference CZTSSe solar cells with an efficiency of 7.29 %, which indicates with improvement of 45 % in efficiency. Consequently, Al doping process is considered as a prospective tactic to elevate the PCE of CZTSSe solar cells.

16.48% Efficient solution-processed CIGS solar cells with crystal growth and defects engineering enabled by Ag doping strategy

Solution-processed Cu(In,Ga)Se2 (CIGS) solar cells suffer from serious carrier recombination and power conversion efficiency (PCE) loss because of the poor film properties and easy formation of defects. Herein, we propose Ag&Se co-selenization strategy to enhance the crystallization and passivate harmful defects of the CIGS films. The formation of Ag-Se phase during the selenization process enables the formation of large grains and suppresses the deep level defects. It is found that Ag doping can enlarge the depletion region width, lower the Urbach energy and prolong the carrier lifetime. As a result, a champion solution-processed CIGS solar cell presents a high efficiency of 16.48% with the highly improved open-circuit voltage (VOC) of 662 mV and fill factor (FF) of 75.8%. This work provides an efficient strategy to prepare high quality solution-processed CIGS films for high-performance CIGS solar cells.

Enhancing electrical and optical properties of anatase TiO2 nanotubes through electrochemical lithiation

In presented paper, anatase TiO2 nanotubes (NTs) were obtained by anodic oxidation of Ti-foil followed by subsequent annealing in air at 400 °C. After thermal treatment, TiO2 nanotubes (NTs) were electrochemically lithiated by means of galvanostatic (GS) discharge, as a part of GS cycling, at 25°C and 55 °C. Microstructural properties of the as-prepared material were observed by scanning and transmission electron microscopy (SEM, TEM), while changes in chemical bonding with lithiation were examined by X-ray photoelectron spectroscopy (XPS). Specific electrical conductivity, obtained by 4-point probe method, showed multifold increase after Li-ion insertion in TiO2 NTs, at both temperatures. By using diffuse reflectance spectroscopy (DRS), the decrease in energy gap, from 3.04 eV for the as-prepared TiO2 NTs to 2.81 eV for lithiated TiO2 NTs, was observed. The photoluminescence (PL) measurements suggest that Li-ion intercalation led to suppression of deep-level trap states within the bandgap, of TiO2 NTs, and promoted shallow defects associated to F-centers. Open-circuit photovoltage decay (OCVD) measurements confirm the promotion of shallow defect states. Furthermore, HER measurements indicate that the electrochemical lithiation is a promising strategy for enhancing the catalytic performance of TiO2.