Metal-organic decomposition growth of thin film metastable perovskite nickelates with kinetically improved quantum transitions

The multiple quantum transitions within d-band correlation oxides such as rare-earth nickelates(RENiO_(3))triggered by critical temperatures and/or hydrogenation opened up a new paradigm for correlated electronics applications,e.g.ocean electric field sensor,bio-sensor,and neuron synapse logical devices.Nevertheless,these applications are obstructed by the present ineffectiveness in the thin film growth of the metastable RENiO_(3)with flexibly adjustable rare-earth compositions and electronic structures.Herein,we demonstrate a metal-organic decompositions(MOD)approach that can effectively grow metastable RENiO_(3)covering a large variety of the rare-earth composition without introducing any vacuum process.Unlike the previous chemical growths for RENiO_(3)relying on strict interfacial coherency that limit the film thickness,the MOD growth using reactive isooctanoate percussors is tolerant to lattice defects and therefore achieves comparable film thickness to vacuum depositions.Further indicated by positron annihilation spectroscopy,the RENiO_(3)grown by MOD exhibit large amount of lattice defects that improves their hydrogen incorporation amount and electron transfers,as demonstrated by the resonant nuclear reaction analysis and near edge X-ray absorption fine structure analysis.This effectively enlarges the magnitude in the resistance regulations in particular for RENiO_(3)with lighter RE,shedding a light on the extrinsic regulation of the hydrogen induced quantum transitions for correlated oxides semiconductors kinetically via defect engineering.

Electronic structure of cuprate-nickelate infinite-layer heterostructure

The discovery of superconductivity in Sr/Ca-doped infinite-layer nickelates Nd(La)NiO_(2)thin films inspired extensive experimental and theoretical research.However,research on the possibilities of enhanced critical temperature by interface heterostructure is still lacking.Due to the similarities of the crystal structure and band structure of infinite-layer nickelate La NiO_(2)and cuprate CaCuO_(2),we investigate the crystal,electronic and magnetic properties of La NiO_(2):CaCuO_(2)heterostructure using density functional theory and dynamical mean-field theory.Our theoretical results demonstrate that,even a very weak inter-layer z-direction bond is formed,an intrinsic charge transfer between Cu-3d_(x^(2)-y^(2))and Ni-3d_((x^(2)-y^(2)))orbitals is obtained.The weak interlayer hopping between Cu and Ni leaves a parallel band contributed by Ni/Cu-3d_((x^(2)-y^(2)))orbitals near the Fermi energy.Such an infinite-layer heterostructure with negligible interlayer interaction and robust charge transfer opens a new way for interface engineering and nickelate superconductors.

Electrochemical ageing study of mixed lanthanum/praseodymium nickelates La2-xPrxNiO4+δ as oxygen electrodes for solid oxide fuel or electrolysis cells

The chemical and electrochemical stability of lanthanide nickelates La2 NiO4+δ(LNO),Pr2 NiO4+δ(PNO)and their mixed compounds La(2-x)PrxNiO4+δ(LPNOs)with x=0.5,1 or 1.5 is reported.The aim is to promote these materials as efficient electrodes for solid oxide fuel cell(SOFC)and/or solid oxide electrolysis cell(SOEC).La2 NiO4+δand La1.5Pr0.5NiO4+δcompounds are chemically very stable as powders over one month in the temperature range 600-800℃,while the other materials rich in praseodymium progressively decompose into various perovskite-deriving components with additional Pr6 O11.Despite their uneven properties,all these materials are quite efficient and sustainable as electrodes on top of gadolinium doped ceria(GDCBL)//yttrium doped zirconia(8 YSZ)electrolyte,for one month at 700℃without polarization.Under polarization(300 mA·cm-2),the electrochemical performances of LNO,PNO and La1.5Pr0.5NiO4+δ(LP5 NO)quickly degrade in SOFC mode,i.e.for the oxygen reduction reaction,while they show durability in SOEC mode,i.e.for the oxide oxidation reaction.

Relevance of 3d multiplet structure in nickelate and cuprate superconductors

The recent discovery of superconductivity in doped rare-earth infinite-layer nickelates RNiO_(2),R=Nd,Pr as a new family of unconventional superconductors has inspired extensive research on their intriguing properties.One of the major motivation to explore the nickelate superconductors originated from their similarities with and differences from the cuprate superconductors,which have been extensively studied over the last decades but are still lack of the thorough understanding.In this short review,we summarized our recent investigation of the relevance of Ni/Cu-3d multiplet structure on the hole doped spin states in cuprate and recently discovered nickelate superconductors via an impurity model incorporating all the 3d orbitals.Further plausible explorations to be conducted are outlined as well.Our presented work provides an insightful framework for the investigation of the strongly correlated electronic systems in terms of the multiplet structure of transition metal compounds.

Theory of unconventional superconductivity in nickelate-based materials

Based on the two-band tight-binding model composed of the 3d orbital of Ni and the 5d orbital of R(=La),we used the random-phase-approximation method to study the pairing symmetry of the nickelate superconductors.It is found that even without considering the coupling between the R and Ni orbitals,neither the antiferromagnetic spin-fluctuation pattern nor the doping-dependent behavior of the robust dx^(2)−y^(2)-wave pairing state obtained in our calculations will be obviously influenced.Our results suggest the dominating role of the Ni 3d orbital in determining the low lying physics of the system.Furthermore,our results reveal a dome-shaped doping dependence of the superconducting transition temperature Tc,which is consistent with recent experiments.

Realization of Low Temperature Densification of Nickelate Ceramics for MLCC Application

We report an improved method for the preparation of highly dense nickelate ceramics at relatively low temperature. It is found that the introduction of appropriate additives during the ball-milling process facilitates the formation of nickelate phase through solid state reaction. Moreover, although high-purity nickelate powders can only be obtained by calcining the mixture of starting materials at temperature higher than 1100 ℃. The adoption of powders calcined at 1000 ℃, rather than those calcined at higher temperature, is conductive to the low-temperature densification of nickelate ceramics, which is attributed to the small and dispersive particles, and the solid state reaction of the residual starting materials during sintering. Compared with the conventional process, the improved method can reduce the sintering temperature of nickelate ceramics by about 100 ℃ and decrease the grain size of the obtained ceramics, and therefore makes nickelate meet the fabrication requirements of multi-layer ceramic capacitors（MLCC）.

Use of Perovskite-Type Lanthanum Nickelate Synthesized by the Polymeric Precursor Method in the Steam Reforming Reaction of Methane

In the current work, LaNiO3 perovskite was synthesized using the polymeric precursor method. The materials were thermally treated at 300°C for 2 hours, subsequently supported on alumina or zirconia and finally calcined at 800°C for 4 hours. The resulting samples were characterized by X-ray diffraction, thermogravimetry, BET surface area and thermo-programmed reduction. Steam reforming reactions were carried out at 750°C and 6 bar during 4 hours using a pilot reactor under a H2O:CH4 ratio of 2.5. The mass of catalysts was about 5.7 g. X-ray diffraction patterns confirmed the formation of the perovskite structure in all samples prepared. The results also showed that lanthanum nickelate was more efficient when supported on alumina than zirconia. Finally, it was observed that the methane conversion was approximately 94% and the selectivity to hydrogen was about 70%. In all cases low selectivity to CO and CO2 was verified.

Correlated perovskite nickelates with valence variable rare-earth compositions

While the metal to insulator transition(MIT)of d-band correlated perovskite nickelates(RENiO_(3))are widely adjustable via their rare-earth composition,the roles of potential valence variabilities associated with the rare-earth elements were rarely concerned.Herein,we demonstrate the material synthesis and MIT properties of RENiO_(3) containing valence variable rare-earth compositions,such as Ce,Pr,Sm,Eu and Tb.The metastable perovskite structure of SmNiO_(3) and EuNiO_(3) with a rare-earth valence states variable towards+2 can be effectively synthesized under high oxygen pressures as it is necessary to reduce their formation free energies.This is in contrast to Ce and Tb,in which situations the variable rare-earth valence state towards+4 reduces their ionic radius and prohibits their occupation or co-occupation of the rare-earth site within the perovskite structured RENiO_(3).Nevertheless,PrNiO_(3) with MIT properties can be effectively synthesized at lower oxygen pressures,owing to the higher stability to form a fully occupied 6s orbit associated Pr3+compared to the half-filled one related to Pr4+.The present work provides guidance for regulating the MIT properties of RENiO_(3).

Superexchange and charge transfer in the nickelate superconductor La_(3)Ni_(2)O_(7) under pressure

Recently, a bulk nickelate superconductor La_(3)Ni_(2)O_(7) is discovered at pressures with a remarkable high transition temperature T_(c)~ 80 K. Here, we study a Hubbard model with tight-binding parameters derived from ab initio calculations of La_(3)Ni_(2)O_(7),by employing large scale determinant quantum Monte Carlo and cellular dynamical mean-field theory. Our result suggests that the superexchange couplings in this system are comparable to that of cuprates. The system is a charge transfer insulator as the hole concentration becomes four per site at large Hubbard U. Upon hole doping, two low-energy spin-singlet bands emerge in the system exhibiting distinct correlation properties: while the one composed of the out-of-plane Ni-d_(3z^(2)-r^(2)) and O-p_(z) orbitals demonstrates strong antiferromagnetic correlations and narrow effective bandwidth, the in-plane singlet band consisting of the Ni-d_(x^(2)-y^(2)) and O-p_(x)/p_(y) orbitals is in general more itinerant. Over a broad range of hole doping, the doped holes occupy primarily the d_(x^(2)-y^(2)) and p_(x)/p_(y) orbitals, whereas the d_(3z^(2)-r^(2)) and p_(z) orbitals retain underdoped. We propose an effective t-J model to capture the relevant physics and discuss the implications of our result for comprehending the La_(3)Ni_(2)O_(7) superconductivity.

Optimization for epitaxial fabrication of infinite-layer nickelate superconductors

The discovery of nickelates superconductor creates exciting opportunities to unconventional superconductivity. However, its synthesis is challenging and only a few groups worldwide can obtain samples with zero-resistance. This problem becomes the major barrier for this field. From plume dynamics perspective, we found the synthesis of superconducting nickelates is a complex process and the challenge is twofold, i.e., how to stabilize an ideal infinite-layer structure Nd_(0.8)Sr_(0.2)NiO_(2), and then how to make Nd_(0.8)Sr_(0.2)NiO_(2) superconducting? The competition between perovskite Nd_(0.8)Sr_(0.2)NiO_(3) and Ruddlesden−Popper defect phase is crucial for obtaining infinite-layer structure. Due to inequivalent angular distributions of condensate during laser ablation, the laser energy density is critical to obtain phase-pure Nd_(0.8)Sr_(0.2)NiO_(3). However, for obtaining superconductivity, both laser energy density and substrate temperature are very important. We also demonstrate the superconducting Nd_(0.8)Sr_(0.2)NiO_(2) epitaxial film is very stable in ambient conditions up to 512 days. Our results provide important insights for fabrication of superconducting infinite-layer nickelates towards future device applications.

Oxygens matter in the bilayer nickelate superconductor

The recent discovery of high T_(c) superconductivity under pressure in a bilayer Ruddlesden-Popper-type nickelate La_(3)Ni_(2)O_(7)[1] has attracted great interest both experimentally and theoretically.Indeed,following this discovery,superconductivity in a trilayer nickelate La_(4)Ni_(3)O_(10) has also been discovered[2,3].These findings have confirmed the arrival of the nickel age of superconductivity[4],kicked off by the discovery of superconductivity in the thin films of infinite layer nickelates[5].

Probing nickelate superconductors at atomic scale:A STEM review

The discovery of nickelate superconductors,including doped infinite-layer(IL)nickelates RNiO2(R=La,Pr,Nd),layered square-planar nickelate Nd6Ni5O12,and the Ruddlesden–Popper(RP)phase La3Ni2O7,has spurred immense interest in fundamental research and potential applications.Scanning transmission electron microscopy(STEM)has proven crucial for understanding structure–property correlations in these diverse nickelate superconducting systems.In this review,we summarize the key findings from various modes of STEM,elucidating the mechanism of different nickelate superconductors.We also discuss future perspectives on emerging STEM techniques for unraveling the pairing mechanism in the“nickel age”of superconductivity.

Frequency regulation in alternation-current transports across metal to insulator transitions of thin film correlated perovskite nickelates

Although the metal to insulator transition(MIT)observed in d-band correlated metal oxides enables promising applications(e.g.,correlated logical devices and Mottronic devices),its present recognition is mainly limited on the direct current(DC)electrical transports.Up to date,the MIT from the perspective of alternation current(AC)transport and its potential electronic applications remains yet unclear.Herein,we demonstrate the frequency(f_(AC))dependence in the impedance(Z=Z’+iZ″)of typical MIT materials,such as thin film rare-earth nickelates(Re NiO_(3)),across the critical MIT temperature(T_(MIT)).Apart from the abrupt change in the impedance modulus(|Z|)across the critical temperature(T_(MIT))similar to the DC transport,the MIT also triggers non-continuous variation in the impedance phase(θ),and this enables the f_(AC)-regulations in the Z’-T tendencies(Z’=|Z|cosθ).At the critical f_(AC) range(e.g.,104-106 Hz),the con-versing variations in|Z|-T and cosθ-T across T_(MIT) result in non-monotonic delta-shape Z’-T tendency in Sm_(x) Nd_(1-x) NiO_(3),the full width half maximum of which is effectively narrowed compared to the situation with the absence of MIT.Further imparting lower or higher f_(AC) elevate the domination in|Z|-T and cosθ-T,respectively,but also enables abrupt Z’-T tendencies across T_(MIT) showing negative temperature coefficient of resistance(NTCR)or positive temperature coefficient of resistance(PTCR).By introducing f_(AC) as a new freedom,the MIT behavior can be more comprehensively regulated electronically,and this extends the vision in exploring the new electronic applications based on the correlated MIT materials from the AC perspective.

Nickelate superconductors get 'hotter'

For more than three decades, the quest for superconductivity in nickel oxides, also known as nickelates, has symbolized the unwavering dedication in search for an analogy to the Nobe Prize-winning high-temperature superconducting copper oxides, or cuprates [1].

Temperature-sensing array using the metal-to-insulator transition of Nd_(x)Sm_(1-x)NiO_(3)

Rare-earth nickelates(RENiO_(3))show widely tunable metal-to-insulator transition(MIT)properties with ignorable variations in lattice constants and small latent heat across the critical temperature(TMIT).Particularly,it is worth noting that compared with the more commonly investigated vanadium oxides,the MIT of RENiO_(3)is less abrupt but usually across a wider range of temperatures.This sheds light on their alternative applications as negative temperature coefficient resistance(NTCR)thermistors with high sensitivity compared with the current NTCR thermistors,other than their expected use as critical temperature resistance thermistors.In this work,we demonstrate the NTCR thermistor functionality for using the adjustable MIT of Nd_(x)Sm_(1-x)NiO_(3)within 200–400 K,which displays larger magnitudes of NTCR(e.g.,more than 7%/K)that is unattainable in traditional NTCR thermistor materials.The temperature dependence of resistance(R–T)shows sharp variation during the MIT of Nd_(x)Sm_(1-x)NiO_(3)with no hysteresis via decreasing the Nd content(e.g.,x≤0.8),and such a R–T tendency can be linearized by introducing an optimum parallel resistor.The sensitive range of temperature can be further extended to 210–360 K by combining a series of Nd_(x)Sm_(1-x)NiO_(3)with eight rare-earth co-occupation ratios as an array,with a high magnitude of NTCR(e.g.,7%–14%/K)covering the entire range of temperatures.

High corrosion and wear resistant electroless Ni–P gradient coatings on aviation aluminum alloy parts

A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.

Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Electrokinetic-mechanism of water and furfural oxidation on pulsed laser-interlaced Cu_(2)O and CoO on nickel foam

The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.

Batch synthesis of rare-earth nickelates electronic phase transition perovskites via rare-earth processing intermediates

The rare-earth nickelates(RENiO_(3)) exhibit an exceptional complex electronic phase diagram and multiple electronic phase transitions that enrich promising applications in correlated electronic devices beyond conventional semiconductors.Nevertheless,the practical applications of RENiO_(3) are challenged by their intrinsic thermodynamic metastability in material synthesis and high material cost.Therefore,developing an economical strategy to achieve the batch synthesis of RENiO_(3) is of vital importance.In this work,we enlarged the synthesis amount of RENiO_(3) up to 20 g per batch using chloride(KCI) assisted molten salt reaction.By optimizing the reaction conditions,the powder of RENiO_(3) with the cubic shape and average size of ~2μm was effectively synthesized,while their phase purity exceeded 95%.In addition,the cost to synthesize RENiO_(3) was further reduced by using rare-earth extraction intermediate products as the raw materials,instead of using the pure rare-earth precursors.It also achieved wide adjustments in the metal-to-insulator-transition temperature from160 to 420 K without significantly reducing the transition sharpness.By enlarging the synthesis amount and the reducing the cost,it paves the way to the device application of RENiO_(3).

Spin excitations in nickelate superconductors

Applying a three-band model and the random phase approximation,we theoretically study the spin excitations in nickelate superconductors,which have been newly discovered.The spin excitations were found to be incommensurate in the low energy region.The spin resonance phenomenon emerged as the excitation energy increased.The intensity can be maximized at the incommensurate or commensurate momentum,depending on the out-of-plane momentum.The spin excitations reverted to incommensurate at higher energies.We also discuss the similarities and differences in the spin excitations of nickelate and cuprate superconductors.Our predicted results can be later validated in inelastic neutron scattering experiments.