Post-deposition Treatment Research Articles

Calcium carbonate particle synthesis in a confined and dynamically thinning layer on a spin-coater – In situ deposition for cell adhesion

We have designed a new method for the in situ synthesis of CaCO3 particles via spin-coating while simultaneously controlling their distribution on the surface. CaCO3 is synthesized by simultaneously adding CaCl2 and Na2CO3 solutions to a rotating surface on a spin-coater. During the transient liquid film evaporation on the spin-coater, as the film layer progressively thins, the CaCO3 particles nucleate and grow while confined within that thinning layer on the spin-coater. The evaporation of the volatile component increases the global concentration of solids, resulting in the deposition of precipitates (CaCO3 particles). The growth rate, particle size, and coverage were theoretically and experimentally analyzed by adjusting the process parameters, initial salt concentrations, rotational speed, and post-deposition treatment. Experimental findings indicated that increasing the rotational speed resulted in formation of smaller particle sizes, while the concentration of the precursors directly influenced the average diameter of the particles. Raman spectroscopy analysis demonstrated that vaterite particles synthesized from lower salt concentrations exhibited a more intense signal than those synthesized from higher salt concentrations. Furthermore, higher salt concentrations led to increased particle coverage, while higher rotational speeds resulted in decreased particle coverage on the substrate. We explored the potential of such coatings in biomedicine and tissue engineering by seeding MC3T3-E1 cells on the CaCO3 particle-coated glass substrates. Surfaces functionalized with CaCO3 particles exhibited enhanced cell proliferation and adhesion.

Quantification of the Stability of ALD-Grown TiO2 Protective Coatings on Photoanodes for Solar Water Splitting

Semiconducting photoabsorbers used in photoelectrochemical applications often exhibit low stability under operating conditions. One strategy implemented in recent years to prevent corrosion of photoelectrodes is the application of thin films of titanium dioxide (TiO2), coated by atomic layer deposition (ALD). However, the stability of these coatings under photoelectrochemical conditions is also limited. We are using spectroscopic ellipsometry (SE) and in-situ atomic force microscope (AFM) characterization[1, 2] in order to quantify the influence of the coating process parameters and of post-deposition treatments on the degradation of these protective layers. Here we show our recent investigations under anodic operation in acidic environment. For fully amorphous TiO2 layers, a significant contributor to the corrosion is a purely chemical process, with an activation energy of 57 kJ/mol. Furthermore, the degradation rate doubles upon illumination under simulated sunlight. With increasing pH, the stability increases significantly. Partially crystalline protective coatings exhibit improved stability under operating conditions in sulfuric acid.

Advances in CIGS thin film solar cells with emphasis on the alkali element post-deposition treatment

Advances in CIGS thin film solar cells with emphasis on the alkali element post-deposition treatment

Impact of tellurium as an anion dopant on the photovoltaic performance of wide-bandgap Cu(In,Ga)Se2 thin-film solar cells with rubidium fluoride post-deposition treatment

The development of wide-bandgap Cu(In,Ga)Se2 thin films is crucial in order to reach the theoretical Shockley–Queisser limit values in single-crystal solar cells. However, the performance of solar cells based on wide-bandgap thin film absorbers has lagged significantly compared to that of their narrow-bandgap counterparts. Herein, we develop a feasible strategy to improve the photovoltaic performance of wide-bandgap Cu(In,Ga)Se2 chalcopyrite thin-film solar cells by simultaneously doping with both RbF PDT and Te2− anions as dopants in the absorber layer during the three-stage co-evaporation process. Besides inducing significant change in the GGI gradient, the synergistic effect of the Te2− anion dopant is rather beneficial in terms of controlling grain size, defects in grain boundaries, and charge carrier lifetime for encouraging charge separation and extraction, which contributes to simultaneously boosting short-circuit current density and fill factor. Te-poor devices afford an impressive efficiency of 9.58%, compared to 6.43% for control devices. More importantly, the efficiency and Voc values obtained for wide-bandgap-based thin-film solar cells containing Te anions were the highest compared to their counterparts as reported in the literature. These results demonstrate the role of Te2− anions in wide-bandgap absorber thin films on the photovoltaic performance of thin-film solar cells and the potential of this approach for use in reasonable and effective design of highly efficient wide-bandgap thin-film solar cells.

Magnetron Sputtering Deposition of High Quality Cs3Bi2I9 Perovskite Thin Films.

Nontoxic all-inorganic perovskites are among the most promising materials for the realization of optoelectronic devices. Here, we present an innovative way to deposit lead-free, totally inorganic Cs3Bi2I9 perovskite from vapor phase. Taking use of a magnetron sputtering system equipped with a radiofrequency working mode power supply and a single target containing the correct ratio of CsI and BiI3 salts, it was possible to deposit a Cs3Bi2I9 perovskitic film on silicon and soda-lime glass. The target composition was optimized to obtain a stoichiometric deposition, and the best compromise was found with a mix enriched with 20% w/w of CsI. Secondly, the effect of post-deposition thermal treatments (150 °C and 300 °C) and of the deposition on a preheat substrate (150 °C) were evaluated by analyzing the chemical composition, the morphology, the crystal structure, and the optical properties. The thermal treatment at 150 °C improved the uniformity of the perovskite film; the one at 300 °C damaged the perovskite deposited. Depositing on a preheated substrate at 150 °C, the obtained film showed a higher crystallinity. An additional thermal treatment at 150 °C on the film deposed on the preheated substrate showed that the crystallinity remains high, and the morphology becomes more uniform.

Gradient doping in Cu2ZnSnSe4 by temperature and potential induced defect steering

Kesterite materials are among the most promising emerging photovoltaic absorbers, despite the number of challenging issues this technology presents. The use of soft thermal post-deposition treatments is key to improving the CdS/kesterite interface quality. Thermal treatments can result in a low-temperature phase transition which affects the optoelectronic properties. In this work, the effects of applied voltage during a full device thermal post-deposition treatments above the critical temperature of the phase transition are explored. The applied voltage modifies the formation energy and drives in-depth migration of ionized defects, which can generate a shallow doping density gradient. Supporting the experimental findings, the effects of a shallow doping density gradient on the current–voltage curves and the external quantum efficiency are modelled using drift–diffusion calculations. The presence of bulk recombination centers in the modelling is a key aspect to precisely reproduce the experimental results. The shallow doping density gradient in opposite directions precisely matches the experimental results for opposite voltage polarizations. The effects on the band structure of the device are presented proving this as a promising strategy for improving charge carrier selectivity.This is the first time that a defect engineering approach has been proposed and successfully proven to control shallow doping density profiling and improve the charge carrier selectivity of kesterite devices. In this sense, the results and their thorough physical interpretation presented in this work will potentially open new perspectives in other photovoltaic technologies as well as in the field of materials engineering.

Thermal annealing of superconducting niobium titanium nitride thin films deposited by plasma-enhanced atomic layer deposition

Next-generation superconducting radio frequency (SRF) cavities, based on tailored thin films, would allow for more efficient and sustainable accelerators operating at higher accelerating gradients. In particular, superconductor–insulator–superconductor (SIS) multilayers are proposed as a potential alternative to bulk Nb. In this context, NbTiN stands out as a superconducting candidate. Here, we report our studies on NbTiN thin films grown by plasma-enhanced atomic layer deposition (PEALD) in a supercycle approach on AlN in situ deposited on planar silicon substrates. In detail, different ternary compound compositions and thicknesses have been investigated concerning the elemental composition, the superconducting properties, and the crystallinity of the deposited thin films. Two different post-deposition thermal treatments have been applied to Nb0.75Ti0.25N thin films of different thicknesses. Their effect on the film properties has been evaluated. It has been demonstrated that an optimized post-deposition thermal annealing procedure significantly improves the quality of our PEALD deposited Nb0.75Ti0.25N thin films, achieving the highest superconducting critical temperature (Tc) of 15.9 K obtained for films deposited by atomic layer deposition (ALD) so far and a lower critical field (Hc1) of 213 mT, which overpasses the bulk Nb intrinsic limit of 200 mT. Our studies are a promising first stepping stone on the path toward tailored thin films based SRF cavities.

Single-Walled Carbon Nanotube (SWCNT) thin films via automatic spray coating and nitric acid vapor treatment

In the realm of optoelectronics to produce thin film, SWCNT (Single-Walled Carbon Nanotube) is a promising alternative to Indium Tin Oxide (ITO). However, it is still challenging to manufacture SWCNT thin film that is low-cost, homogenous and has minimal sheet resistance. In this work, SWCNT thin films were deposited by using the automated spray coating method. To enhance the film quality and optoelectronic characteristics, post-deposition treatment through nitric acid vapor was carried out. The optimized SWCNT thin films exhibited optical transparency in the range of 60.4% at 800 nm and sheet resistance of 6.6 Ω/square. The sheet resistance of our fabricated SWCNT thin films was lower than the value of ITO films (10 Ω/square), putting forth evidence which suggests the potential of SWCNTs as an alternative to ITO.

Enhanced capillary performance of hierarchical dendritic copper surface for ultrathin heat-spreading devices

High-performance electronic systems require efficient heat dissipation devices. Vapor chambers (VCs) are practical thermal solutions for lightweight portable electronics that have limited heat dissipation space. A functional VC requires an interior wick to sustain the capillary circulation of the condensed fluid back to the heated region. The capillary wick performance can be indexed by the ratio of liquid permeability to the effective pore size of the wick structure. This study describes the capillary behavior of a thin hierarchical dendritic copper film (<100 μm thick) prepared by electrodeposition and thermal sintering. The effects of the electrodeposition current density, deposition time, and sintering temperature on the capillary performance of the dendritic copper films were investigated. The relationship between the wicking capability and dendritic morphology, tailored by the electrodeposition process, was explored. A post-deposition sintering treatment was found to be beneficial for improving the structural integrity, adhesion, and capillary performance of dendritic copper wicks. A very high capillary performance (0.81 μm) was realized on a 30-μm-thick dendritic copper wick that matches the need for ultrathin VCs used in highly compact electronic systems.

Reactive Deposition Versus Strong Electrostatic Adsorption (SEA): A Key to Highly Active Single Atom Co-Catalysts in Photocatalytic H2 Generation.

In recent years, the use of single atoms (SAs) has become of a rapidly increasing significance in photocatalytic H2 generation; here SAnoble metals (mainly Pt SAs) can act as highly effective co-catalysts. The classic strategy to decorate oxide semiconductor surfaces with maximally dispersed SAs relies on "strong electrostatic adsorption" (SEA) of suitable noble metal complexes. In the case of TiO2 - the classic benchmark photocatalyst - SEA calls for adsorption of cationic Pt complexes such as [(NH3 )4 Pt]2+ which then are thermally reacted to surface-bound SAs. While SEA is widely used in literature, in the present work it is shown by a direct comparison that reactive attachment based on the reductive anchoring of SAs, e.g., from hexachloroplatinic(IV) acid (H2 PtCl6 )leads directly to SAs in a configuration with a significantly higher specific activity than SAs deposited with SEA - and this at a significantly lower Pt loading and without any thermal post-deposition treatments. Overall, the work demonstrates that the reactive deposition strategy is superior to the classic SEA concept as it provides a direct electronically well-connected SA-anchoring and thus leads to highly active single-atom sites in photocatalysis.

Wire ARC Additive Manufacturing of Functional Metals - A Review

The need for wire arc additive manufacturing (WAAM) has substantially expanded in recent years, and it has emerged as a possible alternative to subtractive production. According to research, the mechanical qualities of wire arc additively manufactured materials are comparable to cast material. When compared to other fusion sources, WAAM provides considerable cost savings as well as a higher deposition rate. However, WAAM presents considerable problems, including undesired microstructures and mechanical characteristics, large residual stresses, and deformation. As a result, more study is required to address the aforementioned problems by optimizing process parameters and post-deposition heat treatment. In accordance with the foregoing, this paper attempts to fill the gap by presenting a comprehensive review of WAAM literature, which includes stage-wise development of WAAM, metals, and alloys used, effects of process parameters, and methodologies used by various researchers to improve the quality of WAAM components. Furthermore, this work suggests topics that could be explored further in the future. Keywords: Wire Arc Additive Manufacturing, Subtractive production, cost saving, optimizing parameters, stage wise development.

Analysis of oxygen-based species introduced during plasma assisted reactive processing of a-IGZO films

Thermal desorption spectroscopy using stable isotopes of 18O2 and D2 was employed to investigate the incorporation and behavior of oxygen-based species in a-IGZO films during plasma assisted processing. Specifically, the behavior of oxygen introduced during deposition with an Ar-18O2 plasma was assessed. The data show that the oxygen amount incorporated in these films during deposition was greatly reduced by a post-deposition plasma treatment. The OD radicals introduced into a-IGZO films deposited with Ar-16O2 during a post-treatment with an Ar + D2 + O2 mixture was also examined. The results indicate that −OD groups in the films were strongly bonded to the metal atoms.

Stability of Cu(InxGa1−x)Se2 Solar Cells Utilizing RbF Postdeposition Treatment under a Sulfur Atmosphere

Alkali halide postdeposition treatments (PDTs) have become a key tool to maximize efficiency in Cu(InxGa1−x)Se2 (CIGS) photovoltaics. RbF PDTs have emerged as an alternative to the more common Na‐ and K‐based techniques. This study utilizes temperature‐dependent current–voltage (JVT) measurements to study a unique RbF PDT performed in a S atmosphere. The samples are measured before and after 6 months in a desiccator to study device stability. Both samples contain Na and K which diffuse from the soda–lime glass substrate. A reference sample and a RbF + S PDT sample both show the development of a rear contact barrier after aging. The contact barrier is higher for the RbF + S PDT sample, leading to decreased current in forward bias. Series resistance is also higher in the RbF + S PDT device which leads to lower fill factor. However, after aging the reference sample has a larger decrease in open‐circuit voltage (VOC). Ideality factor measurements suggest Shockley–Read–Hall recombination dominates both samples. VOC versus temperature and a temperature‐dependent activation energy model are used to calculate diode activation energies for each sample condition. Both techniques produce similar values that indicate recombination primarily occurs within the bulk absorber.

Improvement of carrier transport properties of CsPbBr3 thin films by moisture absorption and TbCl3 doping technique

Moisture absorption and TbCl3 doping of CsPbBr3 thin films were investigated to improve the carrier transport properties. We found that post-deposition moisture-absorbing treatment improved the carrier diffusion length of CsPbBr3 thin films. The moisture-absorbing treatments under a relative humidity of about 20%–40% were effective to improve the carrier diffusion length. TbCl3 doping during the thermal evaporation of CsPbBr3 affected the structure of the deposited films. An excessive amount of TbCl3 doping leads to the formation of CsPb2Br5 additional phase, but a small amount of TbCl3 doping (1%) can improve the carrier diffusion length. The moisture-absorbing treatment and TbCl3 doping are promising techniques to improve the optoelectronic properties of CsPbBr3.

The effect of WC-Co substrates on TiN/TiCN/Al2O3/TiCNO multilayer coatings

ABSTRACT In order to determine optimum substrate, TiN/TiCN/Al2O3/TiCNO coatings were deposited on WC-7Co substrate and WC-6Co substrate (named as Coating-7Co and Coating-6Co, respectively), and then the effect of WC-Co substrates on TiN/TiCN/Al2O3/TiCNO multilayer coatings was investigated by comparing the microstructure, hardness, adhesion strength, oxidation resistance and wear resistance of Coating-7Co and Coating-6Co. Results show that WC grain size of WC-6Co substrate is smaller, correspondingly the grain size of each layer in Coating-6Co is smaller, and the surface roughness is lower. Compared with Coating-7Co, Coating-6Co exhibits higher hardness, better plastic deformation capability, better oxidation resistance, lower friction coefficient and better short-period wear resistance. However, because of higher residual tensile stress and lower adhesion strength, the long-period wear resistance of Coating-6Co is worse than Coating-7Co conversely. To make good use of Coating-6Co, some post-deposition treatment techniques that can reduce residual tensile stress and improve adhesion strength should be considered.

Laser induced crystallization of sputtered MoS2 thin films

The integration of transition metal dichalcogenides (TMDs) thin films into Si CMOS-based devices requires the development of new bottom-up material growth approaches producing high crystallinity films without affecting the SiO2/Si substrate. For this purpose, sputtering is a suitable deposition method due to its simplicity, jointly with high reliability and large area deposition capabilities. However, sputtered layers are amorphous and require a post-deposition thermal treatment to obtain a highly crystalline film. Nanosecond pulsed laser annealing (PLA) has recently emerged as promising route to achieve large-scale crystalline TMDs films without significantly heating or affecting the underlying substrate. The aim of this work is to explore the possibility to produce crystalline 2H–MoS2 on large areas directly on a SiO2-on-Si substrate. The film structure, composition and morphology were monitored as a function of the laser pulse energy density by Raman spectroscopy, X-rays diffraction, Rutherford backscattered spectroscopy (RBS), scanning transmission electron microscopy (STEM) and atomic force microscopy (AFM). The electrical properties of the film with optimized crystallinity were finally investigated through deposition of Cr/Au contacts using shadow masks. This approach can be scaled to other TMDs materials and substrates, also paving the way for the fabrication of heterostructures and electrical devices on the top of a single substrate.

Nanoscale Surface Analysis Reveals Origins of Enhanced Interface Passivation in RbF Post Deposition Treated CIGSe Solar Cells

AbstractAlkali post deposition treatments (PDTs) of Cu(In,Ga)Se2 absorbers have boosted the power conversion efficiency (PCE) of the solar cell devices in the last years. A detailed model explaining how the PDTs impact the optoelectronic properties at the nanoscale is still lacking. Here, via various scanning probe techniques, X‐Ray photo‐electron spectroscopy and high resolution secondary ion mass spectroscopy it is shown that the RbF PDT treatments lead to a one to one exchange of Rb with Cu at the surface. This exchange takes place in the naturally occurring Cu‐depleted CIGSe surface, known as the ordered vacancy compound. A detailed comparison between samples with different PDTs after various cleaning procedures furthermore highlights the necessity to perform all the measurements on NH4OH cleaning surfaces only. After NH4OH, no RbInSe2 phase could be detected at the surface anymore and the surface bandgap, as measured with scanning tunneling spectroscopy is only 1.7 eV. The findings demonstrate that the existence of a RbInSe2 phase is most likely not responsible for the recent improvements in power conversion efficiency for state of the art solar cells. The primary effect of the PDT treatment is a modification of the ordered vacancy compound, where Cu is exchanged with Rb.

Efficiency Improvement of Narrow Band Gap Cu(In,Ga)(S,Se)2 Solar Cell with Alkali Treatment via Aqueous Spray Pyrolysis Deposition

The chalcopyrite Cu(In,Ga)(S,Se)2 (CIGSSe) solar cell with a low band gap is a promising candidate for use as the bottom cell in high-efficiency tandem solar cells. In this study, we investigated narrow band gap CIGSSe solar cells, both with and without alkali treatment. The CIGSSe absorbers were fabricated using aqueous spray pyrolysis in an air environment, with the precursor solution prepared by dissolving constituent metal salts. We found that the power conversion efficiency (PCE) of the fabricated solar cell was significantly enhanced when rubidium postdeposition treatment (PDT) was applied to the CIGSSe absorber. The Rb-PDT facilitates defect passivation and a downshift of the valence band maximum of the CIGSSe absorber, thereby improving the power conversion efficiency and all device parameters. Due to these beneficial effects, a PCE of ∼15% was obtained with an energy band gap of less than 1.1 eV, making it suitable for use as the bottom cell in a highly efficient tandem solar cell.

Influence of growth time on the properties of CdTe thin films grown by electrodeposition using acetate precursor for solar energy application

Cadmium telluride (CdTe) thin films were deposited using a two–electrode electrodeposition (ED) configuration from an aqueous acidic solution. The electrolyte solution contains 1 M of cadmium acetate dihydrate (Cd (CH3OO) 2.2H2O) as cadmium precursor and 1 ml of tellurium dioxide (TeO2) as tellurium precursor. The thin films were grown for different deposition times of 60, 120, 180, 240, and 300 min to investigate the effect of the deposition period on the structural, optical, electrical, surface morphology, elemental composition, and surface roughness properties of the CdTe thin films in both as–deposited and heat–treated forms. X-ray diffraction (XRD) analysis indicates that the CdTe thin films have polycrystalline cubic zinc blend, orthorhombic and hexagonal structures. The result confirmed that the cubic phase is dominant and the peak for preferred orientation is along the (111) plane. Ultraviolet-visible (UV–vis) spectrophotometry study shows that the band gap of the as-deposited thin films varies from (1.41–1.45) eV, and after heat treatment, the band gap decreased to (1.39–1.42) eV. Photoelectrochemical cell (PEC) measurements show that CdTe thin films haven-type conductivity in both as–deposited and annealed forms. Scanning electron microscopy (SEM) analysis shows that the surface morphology of CdTe thin films changed as the deposition period increases. After heat treatment, increase in grain size was observed. Energy–dispersive x-ray spectroscopy (EDS) analysis shows that the percentage composition of as–deposited and heat-treated CdTe thin films varied with deposition time. After post–deposition treatment (PDT), the concentration of Te decreased, while that of Cd increased due to recrystallization during annealing. For the film deposited for 120 min, stoichiometric composition of CdTe was observed after heat treatment. Scanning probe microscopy (SPM) measurements revealed that the average surface roughness of the thin films varied with deposition time. The maximum average surface roughness was recorded when the film was deposited for 120 min. These results show that the prepared CdTe thin films have potential application as absorber layers in thin film solar cells.

Nonradiative Recombination Dominates Voltage Losses in Cu(In,Ga)Se2 Solar Cells Fabricated using Different Methods

Voltage losses reduce the photovoltaic conversion efficiency of thin‐film solar cells and are a primary efficiency limitation in Cu(In,Ga)Se2. Herein, voltage loss analysis of Cu(In,Ga)Se2 solar cells fabricated at three institutions with variation in process, bandgap, absorber structure, postdeposition treatment (PDT), and efficiency is presented. Nonradiative voltage losses due to Shockley–Read–Hall charge carrier recombination dominate and constitute >75% of the total compared to <25% from radiative voltage losses. The radiative voltage loss results from nonideal absorption and carriers in band tails that stem from local composition‐driven potential fluctuations. It is shown that significant bulk lifetime improvements are achieved for all alkali PDT processed absorbers, chiefly associated with reductions in nonradiative recombination. Primary voltage loss contributions (radiative and nonradiative) change little across fabrication processes, but variation in submechanisms (bulk lifetime, net acceptor concentration, and interface recombination) differentiate nonradiative loss pathways in this series of solar cells.