ALD of LaHfOx nano-laminates for high-κ gate dielectric applications

Electrical properties and thermal stability of LaHfO_x nano-laminate films deposited on Si substrates by atomic layer deposition (ALD) have been investigated for future high-κ gate dielectric applications. A novel La precursor, tris(N,N′-diisopropylformamidinato) lanthanum [La(ⁱPrfAMD)₃], was employed in conjunction with conventional tetrakis-(ethylmethyl)amido Hf (TEMA Hf) and water (H₂O). The capacitance-voltage curves of the metal oxide semiconductor capacitors (MOSCAPs) showed negligible hysteresis and frequency dispersion, indicating minimal deterioration of the interface and bulk properties. A systematic shift in the flat-band voltage (V_fb) was observed with respect to the change in structure of nano-laminate stacks as well as La₂O₃ to HfO₂ content in the films. The EOTs obtained were in the range of ∼1.23-1.5 nm with leakage current densities of ∼1.3 × 10⁻⁸ A/cm² to 1.3 × 10⁻⁵ A/cm² at V_fb − 1 V. In addition, the films with a higher content of La₂O₃ remained amorphous up to 950 °C indicating very good thermal stability, whereas the HfO₂ rich films crystallized at lower temperatures.     

Ruthenium oxide metal nanocrystal capacitors with high-κ dielectric tunneling barriers for nanoscale nonvolatile memory device applications

The ruthenium oxide metal nanocrystals embedded in high-κ HfO₂/Al₂O₃ dielectric tunneling barriers prepared by atomic layer deposition in the n-Si/SiO₂/HfO₂/ruthenium oxide (RuO_x)/Al₂O₃/Pt memory capacitors with a small equivalent oxide thickness of 8.6 ± 0.5 nm have been investigated. The RuO_x metal nanocrystals in a memory capacitor structure observed by high-resolution transmission electron microscopy show a small average diameter of ∼7 nm with high-density of >1.0 × 10¹²/cm² and thickness of ∼3 nm. The ruthenium oxide nanocrystals composed with RuO₂ and RuO₃ elements are confirmed by X-ray photoelectron spectroscopy. The enhanced memory characteristics such as a large memory window of ΔV ≈ 12.2 V at a sweeping gate voltage of ±10 V and ΔV ≈ 5.2 V at a small sweeping gate voltage of ±5 V, highly uniform and reproducible, a large electron (or hole) storage density of ∼1 × 10¹³/cm², low charge loss of <7% (ΔV ≈ 4.2 V) after 1 × 10⁴ s of retention time are observed due to the formation of RuO_x nanocrystals after the annealing treatment and design of the memory structure. The charge storage in the RuO_x nanocrystals under a small voltage operation (∼5 V) is due to the modified Fowler-Nordheim tunneling mechanism. This memory structure can be useful for future nanoscale nonvolatile memory device applications.     

Influence of oxidation temperature on the microstructure and electrical properties of Ta2O5 on Si

The effect of the oxidation temperature (673-873 K) on the microstructural and electrical properties of thermal Ta₂O₅ thin films on Si has been studied. Auger electron spectroscopy and X-ray photoelectron spectroscopy results revealed that the films are non-stoichiometric in the depth; an interfacial transition layer between tantalum oxide and Si substrate, containing presumably SiO₂ was detected. It has been found by X-ray diffraction that the amorphous state of Ta₂O₅ depends on both the oxidation temperature and the thickness of the films—the combination of high oxidation temperature (>823 K) and thickness smaller than 50 nm is critical for the appearance of a crystal phase. The Ta₂O₅ layers crystallize to the monoclinic phase and the temperature of the phase transition is between 773 and 823 K for the thinner layers (<50 nm) and very close to 873 K for the thicker ones. The electrical characterization (current/voltage; capacitance/voltage) reveals that the optimal oxidation temperature for achieving the highest dielectric constant (∼32) and the lowest leakage current (10⁻⁸ A/cm² at 1 MV/cm applied field) is 873 K. The results imply that the poor oxidation related defects are rather the dominant factor in the leakage current than the crystallization effects.     

Resistive switching characteristics of ultra-thin TiOx

We investigated the resistive switching characteristics of Ir/TiO_x/TiN structure with 50 nm active area. We successfully formed ultra-thin (4 nm) TiO_x active layer using oxidation process of TiN BE, which was confirmed by X-ray Photoelectron Spectroscopy (XPS) depth profiling. Compared to large area device (50 μm), which shows only ohmic behavior, 250 and 50 nm devices show very stable resistive switching characteristics. Due to the formation and rupture of oxygen vacancies induced conductive filament at Ir and TiO_x interface, bipolar resistive switching was occurred. We obtained excellent switching endurance up to 10⁶ times with 100 ns pulse and negligible degradation of each resistance state at 85 °C up to 10⁴ s.     

First investigation of metal–insulator–metal (MIM) capacitor using Pr2O3 dielectrics

Metal–insulator–metal (MIM) capacitors with Pr₂O₃ as high-k material have been investigated for the first time. We varied the thickness of the Pr₂O₃ layers as well as the bottom electrode material. The layers are characterised using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and secondary ion mass spectroscopy (SIMS). Preliminary information on the interaction of water with the films was obtained from XPS and ab initio pseudopotential calculations. The electrical characterisation shows that Pr₂O₃ MIM capacitors can provide higher capacitance densities than Si₃N₄ MIM capacitors while still maintaining comparable voltage coefficients of capacitance. The Pr₂O₃ dielectric material seems to be suitable for use in silicon RF applications.     

Fabrication and electrical characteristics of ultrathin (HfO2)x(SiO2)1−x films by surface sol-gel method and reaction-anneal treatment

Hafnium oxide (HfO₂) films were deposited on Si substrates with a pre-grown oxide layer using hafnium chloride (HfCl₄) source by surface sol-gel process, then ultrathin (HfO₂)_x(SiO₂)_1−x films were fabricated due to the reaction of SiO₂ layer with HfO₂ under the appropriate reaction-anneal treatment. The observation of high-resolution transmission electron microscopy indicates that the ultrathin films show amorphous nature. X-ray photoelectron spectroscopy analyses reveal that surface sol-gel derived ultrathin films are Hf-Si-O alloy instead of HfO₂ and pre-grown SiO₂ layer, and the composition was Hf_0.52Si_0.48O₂ under 500 °C reaction-anneal. The lowest equivalent oxide thickness (EOT) value of 0.9 nm of film annealed at 500 °C has been obtained with small flatband voltage of −0.31 V. The experimental results indicate that a simple and feasible solution route to fabricate (HfO₂)_x(SiO₂)_1−x composite films has been developed by means of combination of surface sol-gel and reaction-anneal treatment.     

Influence of the metal electrode on the characteristics of thermal Ta2O5 capacitors

The effect of various electrodes (Al, W, TiN) deposited by evaporation (Al) and sputtering (W, TiN) on the electrical characteristics of thermal thin film (15-35 nm) Ta₂O₅ capacitors has been investigated. The absolute level of leakage currents, breakdown fields, mechanism of conductivity, dielectric constant values are discussed in the terms of possible reactions between Ta₂O₅ and electrode material as well as electrode deposition process-induced defects acting as electrically active centers. The dielectric constant values are in the range 12-26 in dependence on both Ta₂O₅ thickness and gate material. The results show that during deposition of TiN and Al a reaction that worsens the properties of Ta₂O₅ occurs while there is not an indication for detectable reduction of Ta₂O₅ when top electrode is W, and the leakage current is 5-7 orders of magnitude lower as compared to Al and TiN-electroded capacitors. The high level of leakage current for TiN and Al gate capacitors are related to the radiation defects generated in Ta₂O₅ during sputtering of TiN, and damaged interface at the electrode due to a reaction between Al and Ta₂O₅, respectively. It is demonstrated that the quality of the top electrode affects the electrical characteristics of the capacitors and the sputtered W is found to be the best. The sputtered W gate provides Ta₂O₅ capacitors with a good quality: the current density <7 × 10⁻¹⁰ A/cm² at 1 V (0.7 MV/cm, 15 nm thick Ta₂O₅). W deposition is not accompanied by an introduction of a detectable damage leading to a change of the properties of the initial as-grown Ta₂O₅ as in the case of TiN electrode. Damage introduced during TiN sputtering is responsible for current deterioration (high leakage current) and poor breakdown characteristics. It is concluded that the sputtered W top electrode is a good candidate as a top electrode of storage capacitors in dynamic random access memories giving a stable contact with Ta₂O₅, but sputtering technique is less suitable (favorable) for deposition of TiN as a metal electrode due to the introduction of radiation defects causing both deterioration of leakage current and poor breakdown characteristics.     

High-k HfO2-Ta2O5 mixed layers: Electrical characteristics and mechanisms of conductivity

Electrical properties of mixed HfO₂-Ta₂O₅ films (10;15 nm) deposited by rf sputtering on Si have been studied from the view point of their applications as high-k layers, by standard capacitance-voltage and temperature dependent current-voltage characteristics. The effect of HfO₂ addition to the Ta₂O₅ is thickness dependent and the thicker layers exhibit advantages over the pure Ta₂O₅ (higher dielectric constant, enhanced charge storage density and improved interface quality). The process of HfO₂ and Ta₂O₅ mixing introduces negative oxide charge, tends to creates shallow bulk traps and modifies the dominant conduction mechanisms in the stack capacitors as compared to the Ta₂O₅-based one (a contribution of tunneling processes through traps located below the conduction band of mixed layers to the leakage current in the HfO₂-Ta₂O₅ stacks is observed). The traps involved in both Poole-Frenkel and tunneling processes are identified.     

Influence of the deposition parameters on the growth of SiGe nanocrystals embedded in Al2O3 matrix

Si_1−xGe_x nanocrystals (NCs), embedded in Al₂O₃ matrix, were fabricated on Si (100) substrates by RF-magnetron sputtering technique with following annealing procedure at 800 °C, in nitrogen atmosphere. The presence of Si_1−xGe_x NCs was confirmed by grazing incidence X-ray diffraction (GIXRD), grazing incidence small angle X-ray scattering (GISAXS) and Raman spectroscopy. The influence of the growth conditions on the structural properties and composition of Si_1−xGe_x NCs inside the alumina matrix was analyzed. Optimal conditions to grow Si_1−xGe_x (x∼ 0.8) NCs sized between 3 and 4 nm in Al₂O₃ matrix were established.     

Intrinsic and extrinsic reliability of a serial connection of capacitors

The on-wafer serial connection of two capacitors (stacked capacitors) is attractive for two reasons: on one hand the intrinsic reliability and especially the immunity against high voltage pulses increases and on the other hand the early fail risk decreases tremendously. The intrinsic and extrinsic reliability of stacked capacitors are demonstrated using the example of a metal insulator metal capacitor (MIMCAP) with Al₂O₃ dielectric. The intrinsic reliability of a stacked capacitor, where each of the capacitors uses a dielectric of thickness thk, is equal to the intrinsic reliability of a single capacitor with twice the dielectric thickness 2 * thk. The reduction of early fails for a stacked capacitor is a probability effect: if a single capacitor has the probability p to fail early and an early fail of the stacked capacitor is the combination of two single capacitors each of which contains an early fail, then the stacked capacitor fails early with a probability of p². This basic idea is checked by voltage ramp experiments on single and stacked MIM capacitors, where the single MIM capacitors show besides the intrinsic branch a prominent extrinsic branch.     

Materials characterization of WNxCy, WNx and WCx films for advanced barriers

A ternary WN_xC_y system was deposited in a thermal ALD (atomic layer deposition) reactor from ASM at 300 °C in a process sequence using tungsten hexafluoride (WF₆), triethyl borane (TEB) and ammonia (NH₃) as precursors. The WC_x layers were deposited by a novel ALD process at a process temperature of 250 °C. The WN_x layers were deposited at 375 °C using bis(tert-butylimido)-bis-(dimethylamido)tungsten (^tBuN)₂(Me₂N)₂W (imido-amido) and NH₃ as precursors. WN_x grows faster on plasma enhanced chemical vapor deposition (PECVD) oxide than WC_x does on chemical oxide. WN_xC_y grows better on PECVD oxide than on thermal oxide, which is opposite of what is seen for WN_x. In the case of the ternary WN_xC_y system, the scalability towards thinner layers and galvanic corrosion behavior are disadvantages for the incorporation of the layer into Cu interconnects. ALD WC_x based barriers have a low resistivity, but galvanic corrosion in a model slurry solution of 15% peroxide (H₂O₂) is a potential problem. Higher resistivity values are determined for the binary WN_x layers. WN_x shows a constant composition and density throughout the layer.     

Electrodepositing ZnxMnyOz alloys from zinc oxide to manganese oxide

Electrodeposition has emerged as a practical and simple method to synthesise semiconductor materials under different forms, thin films or nanostructured layers. This work reports on the cathodic electrodeposition of ZnMnO thin layers using both zinc and manganese chlorides as precursors. The composition of thin films can be varied from binary zinc oxide to manganese oxide varying the Mn/(Mn+Zn) ratio between 0 and 1. The composition of Zn_xMn_yO_z films was obtained by energy dispersive spectroscopy. Zn_1−xMn_xO films with Mn/Zn ratio less than 10% exhibit a crystalline wurtzite structure typical of ZnO fully oriented in the (0 0 2) direction. Higher Mn content leads to deformation of the ZnO lattice and the wurtzite structure is no longer maintained. X-ray photoelectron spectroscopy points out that Mn₃O₄ tends to be deposited when a high Mn/Zn ratio is used in the starting solution. Magnetic measurements on films with Mn/(Zn+Mn) ratio near 1 reveal magnetic characteristics similar to Mn₃O₄ compounds. The transmission spectra of Zn_xMn_yO_z show the typical absorption edge of crystalline ZnO while the wurtzite structure is maintained and it shifts to higher wavelengths when Mn content increases.     

Trap parameters and conduction mechanism in HfO2-Ta2O5 mixed stacks in response to microwave irradiation

The effect of microwave treatment at room temperature on the leakage current and mechanisms of conductivity in mixed HfO₂-Ta₂O₅ (10 nm) stacks has been studied by temperature dependent (20-100 °C) current-voltage characteristics. It was established that the short term irradiation (∼6 s) affects the electrically active centers in the mixed oxide, provokes modification of the dominant conduction mechanism at about and above 1 MV/cm and improves the temperature stability of capacitors manifesting as low level of current at high temperatures (current decrease up to two orders of magnitude at 100 °C after the treatment is detected). The traps involved in the conduction processes in pre- and post-irradiation capacitors are identified. The longer exposure (10-15 s) is effective in a significant reduction of leakage current (up to 3-4 orders of magnitude in wide range of applied voltages). The potential of microwave treatment at room temperature as technological step for improving the temperature stability of leakage current in high-k stacked capacitors is discussed.     

LaScO3 as a higher-κ dielectric for p-MOSFETs

The electrical properties of MOS capacitors with LaScO₃ thin films grown by molecular beam deposition (MBD) have been studied with and without post deposition annealing (PDA) in O₂ environment followed by forming gas. An EOT of 0.65 nm could be achieved for samples without PDA. However, the films suffer from large hysteresis and interface trap density. Applying PDA reduces the hysteresis, the D_it (down to the mid of 10¹¹ (eV cm²)⁻¹) and the leakage current by two orders of magnitude (down to the range of 10⁻⁴A/cm²) for an EOT of 1.1 nm. Furthermore we have successfully integrated LaScO₃ into FD MOSFETs on SOI substrates. The p-FETs with LaScO₃ show excellent characteristics with a steep subthreshold slope down to 65 mV/dec and hole mobilities comparable to HfO₂ and HfSiON.     

Improvement on low-temperature deposited HfO2 film and interfacial layer by high-pressure oxygen treatment

In this study, high-pressure oxygen (O₂ and O₂ + UV light) technologies were employed to effectively improve the properties of low-temperature-deposited metal oxide dielectric films and interfacial layer. In this work, 13 nm HfO₂ thin films were deposited by sputtering method at room temperature. Then, the oxygen treatments with a high-pressure of 1500 psi at 150 °C were performed to replace the conventional high temperature annealing. According to the XPS analyses, integration area of the absorption peaks of O-Hf and O-Hf-Si bonding energies apparently raise and the quantity of oxygen in deposited thin films also increases from XPS measurement. In addition, the leakage current density of standard HfO₂ film after O₂ and O₂ + UV light treatments can be improved from 3.12 × 10⁻⁶ A/cm² to 6.27 × 10⁻⁷ and 1.3 × 10⁻⁸ A/cm² at |Vg| = 3 V. The proposed low-temperature and high pressure O₂ or O₂ + UV light treatment for improving high-k dielectric films is applicable for the future flexible electronics.     

Comparison of short and long wavelength absorption electron donor materials in C60-based planar heterojunction organic photovoltaics

Buckminsterfullerene, C₆₀-based planar heterojunction (PHJ) organic photovoltaics (OPVs) have been created using a short wavelength absorption (λ_max = 490 nm) electron-donating bis(naphthylphenylaminophenyl)fumaronitrile (NPAFN). NPAFN exhibits a hole mobility greater than 0.07 cm² V⁻¹ s⁻¹ as determined by its field-effect transistor. It can be attributed to such hole mobility that enables a thin layer (<10 nm) NPAFN in PHJ OPV, ITO/NPAFN/C₆₀/bathocuproine/Al. Because of the low lying HOMO energy level (5.75 eV) of NPAFN and relatively high ionization potential ITO (∼5.58 eV), such OPVs exhibit a very high open circuit voltage of ∼1.0 V, relatively high fill factor of 0.60, and a relatively high shunt resistance of 1100 Ω cm⁻², which all compensate for a relatively low short circuit current of 3.15 mA cm⁻² due to the short absorption wavelength and inferred short exciton diffusion length of NPAFN. Altogether, NPAFN OPVs display a power conversion efficiency (η_PC) of 2.22%, which is better than other long wavelength absorption materials in similar PHJ OPVs, such as pentacene (λ_max 670 nm, HOMO 5.12 eV, η_PC 1.50%) and copper phthalocyanine (λ_max 624, 695 nm, HOMO 5.17 eV, η_PC 1.43%).     

Changes in effective work function of HfxRu1−x alloy gate electrode

Effective work function (?_m,eff) values of Hf_x Ru_1−x alloy gate electrodes on SiO₂ metal-oxide-semiconductor (MOS) capacitors were carefully examined to assess whether the ?_m,eff was determined by the crystalline structure or the composition of the Hf_xRu_1−x alloy. X-ray diffraction results indicated that the crystalline structures of Hf_xRu_1−x alloy were divided into hexagonal-Ru, cubic-HfRu or hexagonal-Hf with the increase of Hf content. The ?_m,eff values could be controlled continuously from 4.6 to 4.0 eV by changing the Hf content. The experimental ?_m,eff value showed a good agreement with theoretical results considering the compositional ratio of pure Hf and Ru. These results suggest that the ?_m,eff of Hf_xRu_1−x alloy gates on SiO₂ MOS capacitors is dominantly determined by the Hf_xRu_1−x composition rather than the crystalline structure.     

The structural and electrical properties of the SrTa2O6/In0.53Ga0.47As/InP system

The structural and electrical properties of SrTa₂O₆(SrTaO)/n-In_0.53GaAs_0.47(InGaAs)/InP structures where the SrTaO was grown by atomic vapor deposition, were investigated. Transmission electron microscopy revealed a uniform, amorphous SrTaO film having an atomically flat interface with the InGaAs substrate with a SrTaO film thickness of 11.2 nm. The amorphous SrTaO films (11.2 nm) exhibit a dielectric constant of ∼20, and a breakdown field of >8 MV/cm. A capacitance equivalent thickness of ∼1 nm is obtained for a SrTaO thickness of 3.4 nm, demonstrating the scaling potential of the SrTaO/InGaAs MOS system. Thinner SrTaO films (3.4 nm) exhibited increased non-uniformity in thickness. From the capacitance-voltage response of the SrTaO (3.4 nm)/n-InGaAs/InP structure, prior to any post deposition annealing, a peak interface state density of ∼2.3 × 10¹³ cm⁻² eV⁻¹ is obtained located at ∼0.28 eV (±0.05 eV) above the valence band energy (E_v) and the integrated interface state density in range E_v + 0.2 to E_v + 0.7 eV is 6.8 × 10¹² cm⁻². The peak energy position (0.28 ± 0.05 eV) and the energy distribution of the interface states are similar to other high-k layers on InGaAs, such as Al₂O₃ and LaAlO₃, providing further evidence that the interface defects in the high-k/InGaAs system are intrinsic defects related to the InGaAs surface.     

HfAlOx high-k gate dielectric on SiGe: Interfacial reaction, energy-band alignment, and charge trapping properties

Ultra thin HfAlO_x high-k gate dielectric has been deposited directly on Si_1−xGe_x by RF sputter deposition. The interfacial chemical structure and energy-band discontinuities were studied by using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (TOF-SIMS) and electrical measurements. It is found that the sputtered deposited HfAlO_x gate dielectric on SiGe exhibits excellent electrical properties with low interface state density, hysteresis voltage, and frequency dispersion. The effective valence and conduction band offsets between HfAlO_x (E_g = 6.2 eV) and Si_1−xGe_x (E_g = 1.04 eV) were found to be 3.11 eV and 2.05 eV, respectively. In addition, the charge trapping properties of HfAlO_x/SiGe gate stacks were characterized by constant voltage stressing (CVS).     

Analysis of reliability characteristics of high capacitance density MIM capacitors with SiO2-HfO2-SiO2 dielectrics

In this paper, reliability as well as electrical properties of high capacitance density metal-insulator-metal (MIM) capacitor with hafnium-based dielectric is analyzed in depth. The fabricated MIM capacitor exhibits not only high capacitance density but also low voltage coefficient of capacitance (VCC) and low temperature coefficient of capacitance (TCC). It also has a low leakage current level of about ∼1 nA/cm² at room temperature and 1 V. However, it is shown that voltage linearity has a different dependence on the polarity of applied bias as temperature increases maybe due to the bulk traps between the metal electrode and high-k dielectric interface. In addition, the effect of charge trapping and de-trapping on the voltage linearity is analyzed under constant voltage stress.