Hard X-ray Photoelectron Spectroscopy Measurements Research Articles

(Invited) Role of Oxidant Gas for Atomic Layer Deposition of HfxZr1−XO2 Thin Films on Ferroelectricity of Metal-Ferroelectric-Metal Capacitors

Since the first report of ferroelectricity in HfxZr1−xO2 (HZO) in 2011 [1], a lot of attention has been devoted for future non-volatile memory device applications due to its scalability (< 10 nm), low thermal budget (< 400°C) and matured atomic layer deposition (ALD) technique [2]. The thermal ALD process using H2O or O3 is generally employed for the fabrication of ferroelectric HZO thin films. On the other hand, the effect of the plasma-enhanced ALD process using O2 plasma gas on the crystallinity and ferroelectricity has not been systematically clarified. In this paper, we report the importance of ALD oxidant gases for HZO films using H2O or O2 plasma on the ferroelectricity of metal–ferroelectric–metal (MFM) capacitors.MFM capacitors with the H2O- and O2 plasma-based HZO films were fabricated as follows. A 10-nm-thick HZO films were deposited on a TiN bottom-electrode (BE-TiN) by ALD at 300°C using H2O or O2 plasma as oxidant gases and (Hf/Zr)[N(C2H5)CH3]4 (Hf:Zr = 1:1) cocktail precursor. The Hf/Zr ratios in both types of HZO films were estimated to be 0.4/0.6 using X-ray photoelectron spectroscopy (XPS). Next, a post-deposition annealing (PDA) process was carried out at 400 °C for 1 min under a N2 atmosphere. Finally, a TiN top-electrode was deposited by DC sputtering.First, the crystallinity and remanent polarization (2P r = P r + − P r −) of the H2O- and O2 plasma-based HZO films were investigated. Nanocrystals with ferroelectric orthorhombic (O), tetragonal (T), cubic (C) phases partially existed in the O2 plasma-based film after the ALD process, while an amorphous structure dominantly existed in the H2O-based film, analyzed by the grazing-incidence X-ray diffraction analysis and cross-sectional transmission electron microscopy images [3]. This could be because of a strong oxidation power and high energy ion/electron bombardment of O2 plasma. After the PDA process, the O phase was formed more in the O2 plasma-based HZO film than the H2O-based film. Therefore, the nanocrystal grains in the as-grown O2 plasma-based HZO film could play an important role as nuclei for the crystallization and formation of O phase [3,4]. From the polarization–electric field hysteresis curves, the PDA-treated O2 plasma-based capacitor exhibited 2P r of 20 µC/cm2, which was 1.5 times higher than that (13 µC/cm2) of the H2O-based capacitor. Thus, these results indicate that the crystallization and O phase formation of HZO films were promoted by using O2 plasma gas as an ALD oxidant, resulted in a higher 2P r.Next, endurance properties of these MFM capacitors were evaluated. In the wake-up state, both capacitors showed almost the same increase rate (~8%) of switching polarization (P sw). In the fatigued state, on the other hand, the O2 plasma-based capacitor exhibited less P sw degradation (~33%) after 106 cycles, whereas the P sw of H2O-based capacitor decreased by ~47%. To clarify these different fatigue properties, the TiOxNy interface reaction layer (IRL) formation at the HZO/BE-TiN interface was analyzed using synchrotron hard X-ray photoelectron spectroscopy (HAXPES). For the HAXPES Ti 2p spectra, the Ti-O peak intensity for the O2 plasma-based capacitor was larger than that of the H2O-based capacitor [5]. Therefore, an oxygen-rich TiON-IRL could be formed at the HZO/BE-TiN interface during ALD process due to the stronger oxidizing power of O2 plasma. Additional oxygen vacancies (VO) were reported to formed in HfO2-based films during field cycling due to the interface reaction between the HfO2-based film and TiN electrode. Moreover, one of the origins of the P sw degradation was thought to be domain pinning caused by VO [6]. Therefore, an oxygen-rich TiON-IRL for the MFM capacitor with the O2 plasma-based HZO film could prevent the interface reaction and formation of additional VO in HZO films, led to superior fatigue properties.In summary, the MFM capacitor with the O2 plasma-based HZO film showed superior 2Pr and fatigue resistance compared to those of the H2O-based one. Based on these experimental results, it is important to consider the selection of an ALD oxidant for fabrication of HZO-based MFM capacitors.This work was partly supported by JSPS KAKENHI (Nos. JP21J01667, JP20H02189, and JP18J22998) and MEXT Leading Initiative for Excellent Young Researchers (No. JPMXS0320220213). The HAXPES measurements were performed under approval of the NIMS Synchrotron X-ray Station (2020A4602 and 2020A4651).[1] J. Müller et al., Appl. Phys. Lett. 99, 112901 (2011).[2] J.-H. Kim et al., ACS Appl. Electron. Mater. 5, 4726 (2023).[3] T. Onaya et al., APL Mater. 10, 051110 (2022).[4] T. Onaya et al., Microelectron. Eng. 215, 111013 (2019).[5] T. Onaya et al., Solid State Electron. 210, 108801 (2023).[6] M. Pešić et al., Adv. Funct. Mater. 26, 4601 (2016).

Structure-Related Electronic and Magnetic Properties in Ultrathin Epitaxial NixFe3-xO4 Films on MgO(001).

Off-stoichiometric NixFe3-xO4 ultrathin films (x < 2.1) with varying Ni content x and thickness 16 (±2) nm were grown on MgO(001) by reactive molecular beam epitaxy. Synchrotron-based high-resolution X-ray diffraction measurements reveal vertical compressive strain for all films, resulting from a lateral pseudomorphic adaption of the film to the substrate lattice without any strain relaxation. Complete crystallinity with smooth interfaces and surfaces is obtained independent of the Ni content x. For x < 1 an expected successive conversion from Fe3O4 to NiFe2O4 is observed, whereas local transformation into NiO structures is observed for films with Ni content x > 1. However, angle-resolved hard X-ray photoelectron spectroscopy measurements indicate homogeneous cationic distributions without strictly separated phases independent of the Ni content, while X-ray absorption spectroscopy shows that also for x > 1, not all Fe2+ cations are substituted by Ni2+ cations. The ferrimagnetic behavior, as observed by superconducting quantum interference device magnetometry, is characterized by decreasing saturation magnetization due to the formation of antiferromagnetic NiO parts.

Unveiling the Potential of Ambient Air Annealing for Highly Efficient Inorganic CsPbI3 Perovskite Solar Cells.

Here, we report a detailed surface analysis of dry- and ambient air-annealed CsPbI3 films and their subsequent modified interfaces in perovskite solar cells. We revealed that annealing in ambient air does not adversely affect the optoelectronic properties of the semiconducting film; instead, ambient air-annealed samples undergo a surface modification, causing an enhancement of band bending, as determined by hard X-ray photoelectron spectroscopy measurements. We observe interface charge carrier dynamics changes, improving the charge carrier extraction in CsPbI3 perovskite solar cells. Optical spectroscopic measurements show that trap state density is decreased due to ambient air annealing. As a result, air-annealed CsPbI3-based n-i-p structure devices achieved a 19.8% power conversion efficiency with a 1.23 V open circuit voltage.

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V2O5 Double Layers.

The 5/6s2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V2O5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s2 cations situated in interlayer sites between condensed [V4O10]n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered MxV2O5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s2-O 2p-hybridized mid-gap states mediated by second-order Jahn-Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V-V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V-V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg0.5V2O5 and δ-Tl0.5V2O5, respectively, as compared to 7 K for δ-Pb0.5V2O5. In δ-Pb0.5V2O5, the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V4O10] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

Growth chemistry and electrical performance of ultrathin alumina formed by area selective vapor phase infiltration

Abstract 1 1 Commercial equipment is identified in this report in order to specify the experimental procedure adequately and does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor is it intended to imply that the equipment identified is necessarily the best available for the purpose. The growth chemistry and electrical performance of 5 nm alumina films, fabricated via the area-selective vapor phase infiltration (VPI) of trimethylaluminum into poly(2-vinylpyridine), are compared to a conventional plasma enhanced atomic layer deposition (PEALD) process. The chemical properties are assessed via energy dispersive X-ray spectroscopy and hard X-ray photoelectron spectroscopy measurements, while current – voltage dielectric breakdown and capacitance – voltage analysis is undertaken to provide electrical information of these films for the first time. The success and challenges in dielectric formation via polymer VPI, the compatibility of pyridine in such a role, and the ability of the unique and rapid grafting-to polymer brush method in forming coherent metal oxides is evaluated. It was found that VPI made alumina fabricated at temperatures between 200 and 250 °C had a consistent breakdown electrical field, with the best performing devices possessing a к value of 5.9. The results indicate that the VPI approach allows for the creation of alumina films that display dielectric properties of a comparable quality to conventional PEALD grown films. • Dielectrics grown by VPI of poly(2-vinylpyridine) electrically characterised for the first time. • Best performing VPI-made Al 2 O 3 competes in performance to conventional ALD. • IV breakdown reveals a high consistency in electrical properties is possible. • Process is low temperature and compatible in area selective deposition. • CV and HAXPES analysis reveal the next challenges for industry integration.

Molecular beam epitaxy of single-crystalline bixbyite (In1−xGax)2O3 films ( x≤0.18 ): Structural properties and consequences of compositional inhomogeneity

In this work, we show the heteroepitaxial growth of single-crystalline bixbyite (In$_{1-x}$Ga$_x$)$_2$O$_3$ films on (111)-oriented yttria-stabilized zirconia substrates using plasma-assisted molecular beam epitaxy under various growth conditions. A pure In$_2$O$_3$ buffer layer between the substrate and (In$_{1-x}$Ga$_x$)$_2$O$_3$ alloy is shown to result in smoother film surfaces and significantly improved crystallinity. Symmetric out-of-plane 2$\theta - \omega$ x-ray diffraction scans show a single (111) crystal orientation and transmission electron microscopy confirms the single-crystallinity up to $x = 0.18$ and only slight film quality deterioration with increasing Ga content. Partially relaxed layers are demonstrated via reciprocal space mapping with lattice parameters fitting well to Vegard's law. However, the Ga cations are not evenly distributed within the films containing nominally $x > 0.11$: inclusions with high Ga density up to $x = 0.50$ are observed within a "matrix" with $x \approx 0.08$. The cubic bixbyite phase is preserved, in both the "matrix" and the inclusions. Moreover, for $x \geq 0.11$, both the Raman phonon lines as well as the optical absorption onset remain nearly constant. Hard x-ray photoelectron spectroscopy measurements also indicate a widening of the band gap and exhibit similar saturation of the Ga 2p core level position for high Ga contents. This saturation behavior of the spectroscopic properties further supports the limited Ga incorporation into the "matrix" of the film.

Reaction Mechanism of Li2MnO3 Electrodes in an All-Solid-State Thin-Film Battery Analyzed by Operando Hard X-ray Photoelectron Spectroscopy.

Li2MnO3 is a promising cathode candidate for Li-ion batteries because of its high discharge capacity; however, its reaction mechanism during cycling has not been sufficiently explicated. Observations of Mn and O binding energy shifts in operando hard X-ray photoelectron spectroscopy measurements enabled us to determine the charge-compensation mechanism of Li2MnO3. The O 1s peak splits at an early stage during the first charge, and the concentration of lower-valence O changes reversibly with cycling, indicating the formation of a low-valence O species that intrinsically participates in the redox reaction. The O 1s peak-splitting behavior, which indicates the number of valences of O in Li2MnO3, is supported by the computational results for an O3 to O1 structural transition. This is in agreement with the results of our previous study, wherein we confirmed this O3 to O1 transition based on in situ surface X-ray diffraction analysis, X-ray photoelectron spectroscopy, and first-principles formation energy calculations.

Tuning band alignment at a semiconductor-crystalline oxide heterojunction via electrostatic modulation of the interfacial dipole

We demonstrate that the interfacial dipole associated with bonding across the SrTiO3/Si heterojunction can be tuned through space charge, thereby enabling the band alignment to be altered via doping. Oxygen impurities in Si act as donors that create space charge by transferring electrons across the interface into SrTiO3. The space charge induces an electric field that modifies the interfacial dipole, thereby tuning the band alignment from type-II to type-III. The transferred charge, resulting in built-in electric fields, and change in band alignment are manifested in electrical transport and hard x-ray photoelectron spectroscopy measurements. Ab initio models reveal the interplay between polarization and band offsets. We find that band offsets can be tuned by modulating the density of space charge across the interface. Functionalizing the interface dipole to enable electrostatic altering of band alignment opens new pathways to realize novel behavior in semiconducting heterojunctions.

Electrically induced change in HfO2/1-monolayer TiO2/SiO2 metal-oxide-semiconductor stacks: capacitance–voltage and hard X-ray photoelectron spectroscopy studies

Metal-oxide-semiconductor capacitors with HfO2/1-monolayer TiO2/SiO2 stacks were examined to explore the origin of the interface dipole modulation. The capacitance–voltage (C–V) measurements exhibited that the polarity of the interface dipole layer changes depending on the gate bias. The hard X-ray photoelectron spectroscopy measurements demonstrated that an applied gate voltage induces small changes in the Ti–O chemical bonding and potential profile around the HfO2/SiO2 interface.

Electronic structure and small-hole polarons in YTiO3

As a prototypical Mott insulator with ferromagnetic ordering, ${\mathrm{YTiO}}_{3}$ (YTO) is of great interest in the study of strong electron correlation effects and orbital ordering. Here we report the first molecular beam epitaxy (MBE) growth of YTO films, combined with theoretical and experimental characterizations of the electronic structure and charge transport properties. The obstacles of YTO MBE growth are discussed and potential routes to overcome them are proposed. DC transport and Seebeck measurements on thin films and bulk single crystals identify $p$-type Arrhenius transport behavior with an activation energy of $\ensuremath{\sim}0.17\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ in thin films, consistent with the energy barrier for small hole polaron migration from hybrid density functional theory calculations. Hard x-ray photoelectron spectroscopy measurements show the lower Hubbard band at 1.1 eV below the Fermi level, whereas a Mott-Hubbard band gap of $\ensuremath{\sim}1.5\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ is determined from photoluminescence measurements. These findings provide critical insight into the electronic band structure of YTO and related materials.

(Invited) Application of a Laboratory-Based Scanning XPS/Haxpes Instrument for the Characterization of Buried Interfaces

X-ray Photoelectron Spectroscopy (XPS) is a widely used surface analysis technique with many well established industrial and research applications. The surface sensitivity (top 5-10 nm) of XPS and its ability to provide short-range chemical bonding information make the technique extremely popular in materials characterization and failure analysis laboratories. While its surface sensitivity is an important attribute, in some cases, the depth of analysis of XPS is not sufficient to analyze buried interfaces without first sputter etching the sample surface. However, sputter etching can often lead to alterations of the true surface chemistry. An alternative to sputter etching the sample is Hard X-ray Photoelectron Spectroscopy (HAXPES), available at some synchrotron facilities. HAXPES utilizes X-rays typically defined as having energies greater than 5 keV. By increasing the photon energy of the X-ray source, the mean free path of photoelectrons is increased, resulting in an increased information depth obtained from the sample. Depending on the energy used, these hard X-rays can provide depths of analysis three or more times than that of soft x-rays used on conventional XPS systems. HAXPES measurements are, therefore, more sensitive to the bulk, and contributions from the surface are minimized.1,2 This presentation will describe a laboratory-based instrument, the PHI Quantes, equipped with two scanning microprobe monochromated X-ray sources, Al Kα (1486.6 eV) and Cr Kα (5414.9 eV), thus enabling both traditional XPS and HAXPES experiments in the same instrument. Combining both soft and hard X-ray analyses, we can gain an even better understanding of composition with depth and information at buried interfaces. References Kobayashi, K. Hard X-ray photoemission spectroscopy, Nucl. Instr. Meth. Phys. Res. A 2009, 601, 32-47.Fadley, C.S. Hard X-ray Photoemission: An Overview and Future Perspective. In Hard X-ray Photoelectron Spectroscopy (HAXPS); Woicik, J. C., Ed; Springer: Switzerland 2016.

Real-time monitoring the growth of strained off-stoichiometric NixFe3−xO4 ultrathin films on MgO(001)

Ni x Fe 3 − x O4 thin films with varying Ni amount (0 ≤ x ≤ 1.5) were deposited on MgO(001) via reactive molecular beam epitaxy. The growth process was monitored during film deposition by means of X-ray diffraction. All prepared films exhibit a well-ordered structure with complete vertical crystallinity throughout the whole film growth and flat surfaces of the final films independent of the Ni amount. An enhancement of the vertical compression in the initial growth continuously decreases up to a film thickness of 8 nm. During further growth, all films exhibit residual and constant vertical compression with lateral adaption of the final films to the substrate lattice, as observed by high energy surface X-ray diffraction experiments. Hard X-ray photoelectron spectroscopy measurements of the final films reveal increasing Fe3+:Fe2+ ratios for higher Ni content and point to additional NiO agglomerations within the films exceeding the stoichiometric Ni amount of x = 1.

Enhanced magnetization of ultrathin NiFe2O4 films on SrTiO3(001) related to cation disorder and anomalous strain

NiFe$_2$O$_4$ thin films with varying thickness were grown on SrTiO$_3$(001) by reactive molecular beam epitaxy. Soft and hard x-ray photoelectron spectroscopy measurements reveal a homogeneous cation distribution throughout the whole film with stoichiometric Ni:Fe ratios of 1:2 independent of the film thickness. Low energy electron diffraction and high resolution (grazing incidence) x-ray diffraction in addition to x-ray reflectivity experiments were conducted to obtain information of the film surface and bulk structure, respectively. For ultrathin films up to 7.3 nm, lateral tensile and vertical compressive strain is observed, contradicting an adaption at the interface of NiFe$_2$O$_4$ film and substrate lattice. The applied strain is accompanied by an increased lateral defect density, which is decaying for relaxed thicker films and attributed to the growth of lateral grains. Determination of cationic site occupancies in the inverse spinel structure by analysis of site sensitive diffraction peaks reveals low tetrahedral occupancies for thin, strained NiFe$_2$O$_4$ films, resulting in partial presence of deficient rock salt like structures. These structures are assumed to be responsible for the enhanced magnetization of up to $\sim$250\% of the NiFe$_2$O$_4$ bulk magnetization as observed by superconducting quantum interference device magnetometry for ultrathin films below 7.3 nm thickness.

(Invited) Development of Germanium-Tin-Related Semiconductor Heterostructures for Energy Band Design in Electronic and Optoelectronic Applications

Group-IV element semiconductor materials, germanium tin (GeSn) and germanium silicon tin (SiGeSn) have attracted much attention for electronic and optoelectronic applications because of those unique properties; direct transition with a high Sn content, higher carrier mobility than Si and Ge, low growth temperature, and low thermal conductivity [1-3]. GeSiSn realizes the control of energy band structure independently on the lattice constant of alloy. Also, GeSiSn/Ge(Sn) heterostructure provides a type-I energy band alignment with sufficiently large energy band offsets at both conduction and valence band edges simultaneously with the lattice constant matching. That promises an effective carrier confinement structure for quantum well laser and high electron mobility transistor. On the other hand, the development of crystal growth technology for GeSn-related materials is still a challenge, since the thermal equilibrium solid solubilities of Sn in Ge and Si are very low compared to a required substitutional Sn content higher than 10%. It is necessary to understand the behavior of Sn atoms in the epitaxial growth and post deposition process and to control the stability of Sn at substitutional site in GeSn-related epitaxial layers. In addition, the development of interface engineering technology is required for not only GeSn/GeSiSn heterostructure but also metal/GeSn and insulator/GeSn structures for nano-scale electronic devices. Recently, we examined the formation of double heterostructure with GeSiSn/GeSn/GeSiSn layers on Ge substrate using a molecular beam epitaxy (MBE) system [4]. The hard x-ray photoelectron spectroscopy measurement reveals that the sufficiently large energy band offset can be formed at the valence band edge of its GeSiSn/GeSn interface. We also demonstrated that the carrier confinement with this GeSiSn/GeSn/GeSiSn double heterostructure effectively improved the efficiency of photoluminescence (PL) [5]. However, we also found that the crystalline quality of the heteroepitaxial layers significantly influence on the PL intensity and it is necessary to understand the key factor of the crystallinity of heterostructures in order to reduce the dislocation and point defect in the epitaxial layers. For the low temperature growth of GeSn and GeSiSn hetero-epitaxial layers on Ge using MBE, a biaxial compressive strain is often induced into the epitaxial layers, as a GeSn or GeSiSn layer is often grown pseudomorphically on Ge substrate. The compressive strain of GeSn is a disadvantage for enhancing the luminescence efficiency because a higher Sn content is generally required to the indirect-to-direct crossover for a compressively strained GeSn compared to the unstrained case. In order to improve the efficiency of luminescence, it is important not only to enhance the Sn content but also to control the strain structure. We developed the strain relaxation technology of GeSn epitaxial layer on a substrate or buffer layer. We found that the ion implantation into Ge substrate effectively enhance the strain relaxation of GeSn layer. The degree of strain relaxation achieved over 90% for the GeSn layer grown on the Ge substrate after the boron ion implantation with 3x1014 cm-2, while the compressively strained GeSn layer was pseudomorphically grown on the Ge substrate without the ion implantation. This work was partly supported with a Grant-in-Aid for Scientific Research (S) (No. 26220605) and the Core-to-Core Program ICRC-ACP4ULSI from the JSPS.

Anomalous Hall effect and the role of Berry curvature in Co2TiSn Heusler films

Various Co2 based Heusler compounds are predicted to be Weyl materials. These systems with broken symmetry possess a large Berry curvature, and introduce exotic transport properties. The present study on epitaxially grown Co2TiSn films is an initial approach to understand and explore this possibility. The anomalous Hall effect in the well-ordered Co2TiSn films has been investigated both experimentally and theoretically. The measured Hall conductivity is in good agreement to the calculated Berry curvature. Small deviations between them are due to the influence of skew scattering on the Hall effect. From theoretical point of view, the main contribution to the anomalous Hall effect originates from slightly gapped nodal lines, due to a symmetry reduction induced by the magnetization. It has been found that only part of the nodal lines contributed near to the anomalous Hall conductivity at a fixed Fermi energy which can be explained from a magnetic symmetry analysis. Furthermore, from hard x-ray photoelectron spectroscopy measurements, we establish the electronic structure in the film that is comparable to the theoretical density of states calculations. The present results provide deeper insight into the spintronics from the prospect of topology.

Hard x-ray photoelectron spectroscopy study of copper formation by metal salt inclusion in a polymer film

In this work we present the results of a hard x-ray photoelectron spectroscopy (HAXPES) study on the creation of metallic copper layers via metal-salt infiltration into a poly-2-vinylpyridine (P2VP) film. Metal salt inclusion is a wet chemistry process which allows for the fabrication of both metal and metal oxide films by means of infiltrating a receptive polymer thin film with metal salt precursors. A copper infiltrated P2VP film was subject to UV/Ozone treatment to form copper oxide and annealed in-vacuo to reduce the film to metallic copper. HAXPES and transmission electron microscope measurements were used to study the polymer film before and after metal salt infiltration, along with analysis of the copper oxide created after UV/Ozone treatment. The results show successful infiltration of the metal salt into the polymer film, as well as complete conversion to copper oxide following UV/Ozone treatment and reduction to metallic copper with a subsequent in situ anneal, which demonstrates the ability of the technique for the creation of several key integrated circuit features.

Cooperative effects of strain and electron correlation in epitaxial VO2 and NbO2

We investigate the electronic structure of epitaxial VO2 films in the rutile phase using density functional theory combined with the slave-spin method (DFT + SS). In DFT + SS, multi-orbital Hubbard interactions are added to a DFT-fit tight-binding model, and slave spins are used to treat electron correlations. We find that while stretching the system along the rutile c-axis results in a band structure favoring anisotropic orbital fillings, electron correlations favor equal filling of the t2g orbitals. These two distinct effects cooperatively induce an orbital-dependent redistribution of the electron occupations and spectral weights, driving strained VO2 toward an orbital selective Mott transition (OSMT). The simulated single-particle spectral functions are directly compared to V L-edge resonant X-ray photoemission spectroscopy of epitaxial 10 nm VO2/TiO2 (001) and (100) strain orientations. Excellent agreement is observed between the simulations and experimental data regarding the strain-induced evolution of the lower Hubbard band. Simulations of rutile NbO2 under similar strain conditions are performed, and we predict that an OSMT will not occur in rutile NbO2. Our prediction is supported by the high-temperature hard x-ray photoelectron spectroscopy measurement on relaxed NbO2 (110) thin films with no trace of the lower Hubbard band. Our results indicate that electron correlations in VO2 are important and can be modulated even in the rutile phase before the Peierls instability sets in.

Hard X-ray photoelectron spectroscopy investigation of annealing effects on buried oxide in GaAs/Si junctions by surface-activated bonding

Hard X-ray photoelectron spectroscopy measurements are performed on ≈10-nm-thick GaAs film/Si substrate junctions fabricated by the surface activated bonding and selective wet etching. The chemical shifts of GaO and AsO signals in Ga 2p3/2 and As 2p3/2 core spectra indicate that oxides are formed in a part of GaAs films neighboring GaAs/Si interfaces due to the surface activation process. Analyses of GaO and AsO signals show that the thickness of such buried oxides is decreased due to a post-bonding annealing at temperatures up to 400 °C. This means that the electrical properties of bonding interfaces, which are in the meta-stable states, are improved by the annealing. The thickness of oxides is different from that of amorphous-like transition layers at the GaAs/Si interfaces observed by transmission electron microscopy.

Enhanced Carrier Transport and Bandgap Reduction in Sulfur-Modified BiVO4 Photoanodes

Recent progress on bismuth vanadate (BiVO4) has shown it to be among the highest performing metal oxide photoanode materials. However, further improvement, especially in the form of thin film photoelectrodes, is hampered by its poor charge carrier transport and its relatively wide bandgap. Here, sulfur incorporation is used to address these limitations. A maximum bandgap decrease of ∼0.3 eV is obtained, which increases the theoretical maximum solar-to-hydrogen efficiency from 9 to 12%. Hard X-ray photoelectron spectroscopy measurements as well as density functional theory calculations show that the main reason for the bandgap decrease is an upward shift of the valence band maximum. Time-resolved microwave conductivity measurements reveal a ∼3 times higher charge carrier mobility compared to unmodified BiVO4, resulting in a ∼70% increase in the carrier diffusion length. This work demonstrates that sulfur incorporation can be a promising and practical method to improve the performance of wide-bandgap metal oxide photoelectrodes.

Characterization of electron charging and transport properties of Si-QDs with phosphorus doped Ge core

We formed high-density Si quantum dots (Si-QDs) with undoped and P-doped Ge cores on thermally-grown SiO2 by controlling low pressure chemical vapor depositions of Si and Ge. Doping into the Ge core was carried out during selective-growth of Ge on pre-grown Si-QDs. From hard x-ray photoelectron spectroscopy measurements, we confirmed phosphorus incorporation into the Ge core, where phosphorus donor concentration in the Ge core was roughly estimated to be ∼0.09 at%. When the surfaces of Si-QDs with undoped and P-doped Ge cores were scanned with an Rh-coated tip biased at 0 V, the surface potential of Si-QDs with P-doped Ge cores were increased by ∼30 mV, while that of Si-QDs with undoped Ge cores remained unchanged. These results indicate that an electron was extracted from the conduction band of the Ge core due to a phosphorus donor. In the current images measured with the Rh-coated tip, the current level of Si-QDs with P-doped Ge cores on n-Si(100) substrates was higher than that of Si-QDs with undoped Ge cores. This result indicates that phosphorus donor can contribute to an increase in the electron injection rate from the Si-substrate.