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The incessant downscaling of building blocks for memory and logic in computer chips requires energy-efficient devices. Thermoelectric-based temperature sensing, cooling as well as energy harvesting could be useful methods to reach reliable device performance with stable operating temperatures. For these applications, complementary metal–oxide–semiconductor (CMOS)-compatible and application ready thin films are needed and have to be optimized. In this work, we investigate the power factor of different phosphorous-doped silicon germanium (SiGe) films fabricated in a 300 mm CMOS-compatible cleanroom. For the thermoelectric characterization, we used a custom-built setup to determine the Seebeck coefficient and sheet resistance. For sample preparation, we used low pressure chemical vapor deposition with in situ doping and subsequent rapid thermal annealing on 300 mm wafers. Thin film properties, such as film thickness (12–250 nm), elemental composition, crystallinity, and microstructure, are studied via spectroscopic ellipsometry, x-ray photoelectron spectroscopy, x-ray diffraction, atomic force microscopy, and TEM. The SiGe-based thin films vary in the ratio of Si to Ge to P and doping concentrations. A power factor of 0.52 mW/m K2 could be reached by doping variation. Our results show that SiGe is a very attractive CMOS-compatible material on the 300 mm wafer level and is immediately ready for production of thermoelectric embedded applications. [ABSTRACT FROM AUTHOR]

The hafnium oxide (HfO2) material system offers a unique combination of outstanding physical properties, that enable a manifold of novel integrated ferroelectric, piezoelectric, and pyroelectric applications. Long‐term stability is an essential concern for nonvolatile memory devices, sensors, and nanoelectromechanical systems. Herein, the aging effects of the pyroelectric response in polycrystalline Si‐doped HfO2 thin films in the field‐free case are reported. It is observed that aging effects are accelerated by high temperatures, lower film thicknesses, and higher dopant concentration. The decay of the pyroelectric coefficients and the dielectric permittivity exhibits a logarithmic time dependence. The full pyroelectric response is restored by repeated electric field cycling (i.e., deaging). After the aging process, a significant internal bias field is observed. It is concluded that the migration of positively charged oxygen vacancies in the films is responsible for this aging process. [ABSTRACT FROM AUTHOR]

The hafnium oxide material class is characterized by the coexistence of several polymorphs between which phase transitions are induced by means of composition and external electric fields. Pyroelectric materials, which convert heat into electrical energy, exhibit the largest response at such morphotropic or field-induced phase transitions. The hafnium oxide material system is of special interest for pyroelectric applications since it allows for scalable and semiconductor-compatible fabrication. Here, we report large pyroelectric coefficients at the morphotropic transition from the ferroelectric orthorhombic to the centrosymmetric tetragonal phase. The electric field-induced transition between these two phases in doped HfO2 is found to yield large pyroelectric coefficients of up to −142 µCm−2 K−1, a value that is 20 times larger compared to AlN. [ABSTRACT FROM AUTHOR]

In this Letter, we report the percentage of the ferroelectric phase in a 10-nm-thick Hf0.5Zr0.5O2 (HZO) film deposited in a metal-insulator-metal stack by atomic layer deposition. The ferroelectric behavior was confirmed by polarization measurements and piezoresponse force microscopy. Ferroelectric behavior in this material has been attributed most likely to the formation of the polar non-centrosymmetric orthorhombic phase [Müller et al., Appl. Phys. Lett. 99, 102903 (2011)], which is difficult to distinguish from the tetragonal phase in x-ray diffraction due to peak overlap. Using a model for each of the crystal phases of hafnia-zirconia, the phase percentages were estimated using a Rietveld refinement method applied to grazing incidence x-ray diffraction data and a linear combination fit analysis procedure [McBriarty et al., Phys. Status Solidi 257, 1900285 (2020)] applied to grazing incidence extended x-ray absorption fine structure data. Using these methods, it was found that the tetragonal (P42/nmc) phase is the most prevalent at 48–60% followed by the polar non-centrosymmetric orthorhombic (Pca21) phase at 35%–40% with the remainder consisting of the monoclinic (P21/c) phase. Understanding the details of the effect of the phase structure on the electrical properties of these materials is extremely important for device engineering of HZO for logic and emerging nonvolatile memory applications. [ABSTRACT FROM AUTHOR]

Metal-Insulator-Metal capacitors, with ZrO2/Al2O3/ZrO2 (ZAZ)-nanolaminate thin-films as a dielectric layer, exhibit reduced leakage currents compared to corresponding capacitors based on pure ZrO2 while maintaining a sufficiently high dielectric constant for the DRAM application. This work is a comparative study demonstrating how the incorporation of a small amount of Al is responsible for the suppression of crystallization during deposition. Extensive electrical characterization leads to the identification of a defect band which conductive atomic force microscopy shows to be formed along crystallite grain boundaries, extending through the entire ZrO2-film. The incorporation of a sub-layer of Al2O3 prevents these grain boundaries resulting in an effective reduction of leakage currents, despite the film being in the nanocrystalline phase, necessary for it to exhibit the required high dielectric constant. A transport model based on phonon assisted trap to trap tunneling is proposed. [ABSTRACT FROM AUTHOR]

Herein, growth kinetics, crystal structure, and the uniformity of titanium oxide (TiO2) thin films prepared using atomic layer deposition (ALD) and plasma‐enhanced ALD (PE‐ALD) are studied. TiO2 thin films are grown using titanium tetrachloride (TiCl4), water, and oxygen precursors. Using ALD, TiO2 is grown in the temperature range of 270–310 °C thermally and in the range of 300–400 °C with PE‐ALD. In spite of the plasma process yielding better uniformity on planar structures, the optimized thermal process provides a remarkable conformal step coverage within deep trenches. In addition, the change in the crystal structure and phase transitions of TiO2 is presented herein. This is attempted at using TiO2 as a component material to grow lithium titanate (LTO) as an electrode material in solid‐state lithium‐ion batteries (LIBs). Thereby, different substrates are used. In comparison to the silicon (Si) substrate, silicon oxide (SiO2) and titanium nitride (TiN) lead to crystal phase transformation while annealing. Measurements are performed using in situ high‐temperature X‐ray diffraction (HT‐XRD). It is also shown that when TiN is sandwiched between TiO2 and the silicon substrate, the TiO2 thin film (25 nm) gradually changes from an anatase to a rutile structure. [ABSTRACT FROM AUTHOR]

The in‐plane piezoelectric response of 20 nm thick Si‐doped HfO2 is examined by exploiting thermal expansion of the substrate upon rapid temperature cycling. The sample is heated locally by a deposited metal film, and the subsequently registered pyroelectric current is found to be frequency dependent in the observed range of 5 Hz to 35 kHz. While the intrinsic response remains constant, the secondary contribution can be switched off in the high‐frequency limit due to substrate clamping. As this secondary response is generated by thermal expansion and the piezoelectric effect, this allows for extraction of the corresponding in‐plane response. By comparing pyroelectric measurements in low‐ and high‐frequency limits, a piezoelectric coefficient d31 of −11.5 pm V −1 is obtained, which is more than five times larger than that of AlN. The magnitude of piezoelectric response increases upon electric field cycling, which is associated with a transition from antiferroelectric‐like behavior to a purely ferroelectric polarization hysteresis. The hafnium oxide material system is proposed as a promising candidate for future CMOS compatible piezoelectric micro‐ and nano‐electromechanical systems (MEMS and NEMS). [ABSTRACT FROM AUTHOR]

In this paper, we investigate the influence of electrode roughness on the leakage current in TiN/high-κ ZrO2/TiN (TZT) thin-film capacitors which are used in dynamic random access memory cells. Based on a microscopic transport model, which is expanded to incorporate electrode roughness, we assess the ultimate scaling potential of TZT capacitors in terms of equivalent oxide thickness, film smoothness, thickness fluctuations, defect density and distribution, and conduction band offset (CBO). The model is based on three-dimensional, fully self-consistent, kinetic Monte Carlo transport simulations. Tunneling transport in the bandgap of the dielectric is treated, which includes defect-assisted transport mechanisms. Electrode roughness is described in the framework of fractal geometry. While the short-range roughness of the electrodes is found not to influence significantly the leakage current, thickness fluctuations of the dielectric have a major impact. For thinner dielectric films they cause a transformation of the dominant transport mechanism from Poole-Frenkel conduction to trap-assisted tunneling. Consequently, the sensitivity of the leakage current on electrode roughness drastically increases on downscaling. Based on the simulations, optimization of the CBO is suggested as the most viable strategy to extend the scalability of TZT capacitors over the next chip generations. [ABSTRACT FROM AUTHOR]

The capacitance behavior of metal insulator metal (MIM) structures with Zr1-xAlxO2 dielectrics and TiN metal electrodes is analyzed. The capacitance nonlinearity, the dielectric relaxation, and the loss phenomena are found to depend strongly on the Al content, the dielectric thickness, and the amorphous/crystalline phase of the dielectric layer. Two different kinds of phenomena—crystallization-related and interface-related, are considered to explain the observed results, especially the polarity asymmetry in the dielectric behavior. It is found that crystallization of the films enhances the effects of dielectric relaxation and loss, most likely due to charge trapping at grain boundaries. Further on, reactions between the oxidizing ambient (ozone) and the bottom electrode during high-k deposition result in structural changes (formation of TiOx interfacial layer) and thus in generation of defects which cause a different electrical behavior of the two TiN/Zr1-xAlxO2 interfaces at the top and the bottom electrode and a polarity asymmetry of the capacitance performance. [ABSTRACT FROM AUTHOR]

The capacitance behavior of metal insulator metal (MIM) structures with [Zr.sub.1-x][Al.sub.x][O.sub.2] dielectrics and TiN metal electrodes is studied. The reactions between the oxidizing ambient and the bottom electrode during high-k deposition has resulted in structural changes and thus in generation of defects that cause a different electrical behavior of the two TiN/[Zr.sub.1-x][Al.sub.x][O.sub.2] interfaces at the top and the bottom electrode and a polarity asymmetry of the capacitance performance.

Lithium titanate (Li4Ti5O12) (LTO) has several promising properties with regard to energy storage. The most important is its low volume expansion during lithium (de-) intercalation enabling the material for complex three-dimensional battery anode designs. To employ this property at a small scale, e.g., for micro batteries (<100 nm active layer thickness), a highly conformal deposition process like atomic layer deposition (ALD) is needed. However, the ALD of lithium containing layers is quite ambitious. Particularly, thermally activated deposition of lithium containing layers with water as a coreactant is challenging due to the high reactivity and hygroscopic nature of many lithium compounds, e.g., lithium hydroxide. That is why a novel ALD process regime has been developed, which allows the deposition of highly conformal and single phase LTO layers with excellent step coverage and composition. The process uses two metalorganic precursors: one acting as lithium and another as a titanium source. In contrast to usual ALD processes, these two precursors are subsequently applied. The reactive pulse with water is applied after the two metal precursor pulses. In this work, this novel ALD process sequence has been introduced and successfully demonstrated on 200 mm wafers using standard industrial ALD equipment. The layers are transformed to single phase Li4Ti5O12 by rapid thermal processing as proven by crystal phase analysis. Elemental composition has been analyzed by time of flight secondary ion mass spectrometry and x-ray photoelectron spectroscopy (XPS). Results show that the amounts of contaminants like carbon and chlorine are below the detection limits of XPS. Also, a uniform element distribution and stoichiometry in good agreement with theoretical expectations for lithium titanate could be shown. [ABSTRACT FROM AUTHOR]

Capacitors based on 10 nm antiferroelectric silicon-doped hafnium oxide (Si:HfO2) thin films are investigated in terms of energy storage efficiency, cycling endurance, and reliability. Atomic layer deposition (ALD) on an area-enhanced substrate with large-scale arrays of deep-trench structures is used to significantly increase the energy density, yielding a value of 450 μJ/cm2 and an energy storage efficiency of 67% at a voltage of 3 V. High breakdown fields are obtained, and the reliability measurement indicates that more than 90% of the devices survive three years when subjected to an operating voltage of 3 V. The film stoichiometry is optimized in terms of energy storage properties to achieve an antiferroelectric-like hysteresis loop with low fatigue during electric field cycling and uniform electrical characteristics throughout the 300 mm wafer. Si:HfO2 is a promising material for novel integrated energy storage applications, as it combines CMOS compatible manufacturing, high scalability, and conformal deposition using ALD. [ABSTRACT FROM AUTHOR]

ZrO2-based metal-insulator-metal capacitors are used in various volatile and nonvolatile memory devices as well as for buffer capacitors or radio frequency applications. Thus, process optimization and material tuning by doping is necessary to selectively optimize the electrical performance. The most common process for dielectric fabrication is atomic layer deposition which guarantees high conformity in three dimensional structures and excellent composition control. In this paper, the C-V and J-V characteristics of ZrO2 metal-insulator-metal capacitors with TiN electrodes are analyzed in dependence on the O3 pulse time revealing the optimum atomic layer deposition process conditions. Moreover, a detailed study of the leakage current mechanisms in undoped ZrO2 compared to SiO2- or Al2O3-doped ZrO2 is enclosed. Thereby, the discovered dependencies on interfaces, doping, layer thickness, and crystalline phase's enable the detailed understanding and evaluation of the most suitable material stack for dynamic random access memory devices below the 20 nm generation. [ABSTRACT FROM AUTHOR]

Leakage currents in \TiN/\high-\kappa\-ZrO2/ \TiN capacitors were simulated by using a novel kinetic Monte Carlo algorithm specially designed to describe tunneling transport of charge carriers in high-\kappa dielectrics, including defect-assisted transport mechanisms. Comparing simulation results with experimental data, a model for electronic transport was established and validated. Transport was found to be dominated by Poole–Frenkel emission from positively charged bulk trap states at medium voltages and trap-assisted tunneling at high voltages. Information on the conduction band offset at the \TiN/ZrO2 interface as well as on the trap depth was extracted. The model accurately describes the scaling of the leakage current with temperature and with thickness of the dielectric film, and it provides insight into the mutual interdependence of the competing transport mechanisms. [ABSTRACT FROM AUTHOR]

In order for sub-10 nm thin films of ZrO2 to have a dielectric constant larger than 30 they need to be crystalline. This is done by either depositing the layer at higher temperatures or by a postdeposition annealing step. Both methods induce high leakage currents in ZrO2 based dielectrics. In order to understand the leakage a thickness series of ultrathin ZrO2 and nanolaminate ZrO2/Al2O3/ZrO2 (ZAZ) films, deposited by atomic layer deposition, was investigated. After deposition these films were subjected to different rapid thermal annealing (RTA) processes. Grazing incidence x-ray diffraction and transmission electron microscopy yield that the crystallization of ZrO2 during deposition is dependent on film thickness and on the presence of an Al2O3 sublayer. Moreover, the incorporation of Al2O3 prevents crystallites from spanning across the entire film during RTA. C-V and I-V spectroscopies show that after a 650 °C RTA in N2 the capacitance equivalent oxide thickness of 10 nm ZAZ films is reduced to 1.0 nm while maintaining low leakage currents of 3.2×10-8 A/cm2 at 1 V. Conductive atomic force microscopy studies yield that currents are not associated with significant morphological features in amorphous layers. However, after crystallization, the currents at crystallite grain boundaries are increased in ZrO2 and ZAZ films. [ABSTRACT FROM AUTHOR]

Abstract: In the photovoltaic industry the etching of silicon in HF/HNO3 solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO3 etch solutions including the reaction product H2SiF6 have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO3)3 are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H2SiF6 at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF6 2− anion and titrated in absence of buffers. In a second method, the titration with La(NO3)3 is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control. [Copyright &y& Elsevier]

We report on a simulation algorithm, based on kinetic Monte Carlo techniques, that allows us to investigate transport through high-permittivity dielectrics. In the example of TiN/ZrO2/TiN capacitor structures, using best-estimate physical parameters, we have identified the dominant transport mechanisms. Comparison with experimental data reveals the transport to be dominated by Poole–Frenkel emission from donorlike trap states at low fields and trap-assisted tunneling at high fields. [ABSTRACT FROM AUTHOR]

High-k dielectric layers (HfSixOy and ZrO2) with different film morphologies were investigated by tunneling atomic-force microscopy (TUNA). Different current distributions were observed for amorphous and nanocrystalline films by analyzing TUNA current maps. This even holds for crystalline layers where highly resolved atomic-force microscopy cannot detect any crystalline structures. However, TUNA enables the determination of morphology in terms of differences in current densities between nanocrystalline grains and their boundaries. The film morphologies were proven by high-resolution transmission electron microscopy. The investigations show TUNA as powerful current mapping tool for the characterization of morphology in thin high-k films on a nanoscale. [ABSTRACT FROM AUTHOR]

For the analysis of thin films, with high aspect ratio (HAR) structures, time-of-flight secondary ion mass spectrometry (ToF-SIMS) overcomes several challenges in comparison to other frequently used techniques such as electron microscopy. The research presented herein focuses on two different kinds of HAR structures that represent different semiconductor technologies. In the first study, ToF-SIMS is used to illustrate cobalt seed layer corrosion by the copper electrolyte within the large through-silicon-vias (TSVs) before and after copper electroplating. However, due to the sample's surface topography, ToF-SIMS analysis proved to be difficult due to the geometrical shadowing effects. Henceforth, in the second study, we introduce a new test platform to eliminate the difficulties with the HAR structures, and again, use ToF-SIMS for elemental analysis. We use data image slicing of 3D ToF-SIMS analysis combined with lateral HAR test chips (PillarHall™) to study the uniformity of silicon dopant concentration in atomic layer deposited (ALD) HfO2 thin films. [ABSTRACT FROM AUTHOR]

ZrO2 is of very high interest for various applications in semiconductor industry especially as high-k dielectric in metal-insulator-metal (MIM) capacitor devices. Further improvement of deposition processes, of material properties, and of integration schemes is essential in order to meet the strict requirements of future devices. In this paper, the authors describe a solution to solve one of the key challenges by reducing the process time of the bottle neck high-k atomic layer deposition (ALD). The authors extensively optimized the most common ALD process used for the ZrO2 deposition (TEMAZ/O3) resulting now in a doubled growth rate compared to the published growth rates of maximum 1 Å/cycle. Chemical reactions explaining the origin of the high growth rate are proposed by theoretical process modelling. At the same time, the outstanding electrical properties of ZrO2 thin films could be preserved. Finally, the integration of the ZrO2 process in MIM capacitor devices with TiN electrodes was evaluated. Thereby, the known effect of TiN bottom electrode oxidation by the O3 process was analyzed and significantly reduced by different integration approaches including wet chemical treatments and ALD process variations. The resulting MIM capacitors show low leakage current and high polarity symmetry. [ABSTRACT FROM AUTHOR]

Thin ZrO2 films are of high interest as high-k material in dynamic random access memory (DRAM), embedded dynamic random access memory, and resistive random access memory as well as for gate oxides. Actually, ZrO2 is predicted to be the key material in future DRAM generations below 20 nm. Profound knowledge of pure and doped ZrO2 thin films, especially of the structural properties, is essential in order to meet the requirements of future devices. This paper gives a detailed overview about the structural properties of ZrO2 films in dependence of various process parameters. The study of atomic layer deposition (ALD) growth mechanisms of ZrO2 on a TiN-substrate in comparison to a Si-substrate covered with native oxide exhibits significant differences. Furthermore, the structural properties crystallinity, surface roughness, and film stress are studied after the ALD deposition in dependence of the process parameters deposition temperature, layer thickness, and underlying substrate. Remarkable dependencies of the ZrO2 crystallization temperatures on the substrates are figured out. The structural properties after various annealing steps are monitored as well. The influence of doping by SiO2 and Al2O3 is studied, which is primarily used to keep the thin films amorphous during deposition. [ABSTRACT FROM AUTHOR]

We assess the impact of structural relaxation of defects upon charging on trap-assisted tunneling in high-κ dielectric materials. Zr02/Al203/Zr02 thin films are taken as an exemplary system. In our completely different approach, a first-principles defect model is derived from Hedins GW approximation calculations, which is then coupled to kinetic Monte Carlo charge transport simulations. Comparison between simulation and experiment demonstrates that it is often imperative to take structural relaxation processes into account when modeling nanoscale transport across defect states. [ABSTRACT FROM AUTHOR]

Upcoming energy-autonomous mm-scale Internet-of-things devices require high-energy and high-power microbatteries. On-chip 3D thin-film batteries (TFBs) are the most promising option but lack high-rate anode materials. Here, Li 4 Ti 5 O 12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated on 3D substrates for the first time. The 3D Li 4 Ti 5 O 12 reveals an excellent footprint capacity of 20.23 µAh cm -2 at 1 C. The outstanding high-rate capability is demonstrated with 7.75 µAh cm -2 at 5 mA cm -2 (250 C) while preserving a remarkable capacity retention of 97.4% after 500 cycles. Planar films with various thicknesses exhibit electrochemical nanoscale effects and are tuned to maximize performance. The developed ALD process enables conformal high-quality spinel (111)-textured Li 4 Ti 5 O 12 films on Si substrates with an area enhancement of 9. Interface engineering by employing ultrathin AlO x on the current collector facilitates a required crystallization time reduction which ensures high film and interface quality and prospective on-chip integration. This work demonstrates that 3D Li 4 Ti 5 O 12 by ALD can be an attractive solution for the microelectronics-compatible fabrication of scalable high-energy and high-power Li-ion 3D TFBs., (© 2024 The Author(s). Small published by Wiley-VCH GmbH.)

The "zero-strain" Li 4 Ti 5 O 12 is an attractive anode material for 3D solid-state thin-film batteries (TFB) to power upcoming autonomous sensor systems. Herein, Li 4 Ti 5 O 12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated for the first time. The developed ALD process with a growth per cycle of 0.6 Å cycle -1 at 300 °C enables high-quality and dense spinel films with superior adhesion after annealing. The short lithium-ion diffusion pathways of the nanostructured 30 nm films result in excellent electrochemical properties. Planar films reveal 98% of the theoretical capacity with 588 mAh cm -3 at 1 C. Substrate-dependent film texture is identified as a key tuning parameter for exceptional C-rate performance. The highly parallel grains of a strong out-of-plane (111)-texture allow capacities of 278 mAh cm -3 at extreme rates of 200 C. Outstanding cycle performance is demonstrated, resulting in 97.9% capacity retention of the initial 366 mAh cm -3 after 1000 cycles at 100 C. Compared to other deposition techniques, the superior performance of ALD Li 4 Ti 5 O 12 is a breakthrough towards scalable high-power 3D TFBs., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

In the photovoltaic industry the etching of silicon in HF/HNO(3) solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO(3) etch solutions including the reaction product H(2)SiF(6) have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO(3))(3) are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H(2)SiF(6) at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF(6)(2-) anion and titrated in absence of buffers. In a second method, the titration with La(NO(3))(3) is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control.