Electrical characterisation of HfYO MIM-structures deposited by ALD

By an ALD process with the solid precursors HfCl₄ and (CpCH₃)₃Y and the oxidant water Yttrium doped HfO₂ was deposited on TiN layer on highly doped silicon. The films were analysed by ellipsometry, XRR, RBS and XRD. For the electrical characterisation, capacitance and I-V measurement on MIM structure were used. By doping the HfO₂ with 6.2 at.% Yttrium and annealing the film at 500 °C in N₂ the k-value increased by 60% for a 9.5 nm thick film, the leakage current also increased. The deposited amorphous film crystallises at 450 °C into the cubic phase.     

Effects of substrate temperature on dielectric and structural properties of Ti and Er co-doped HfO2 thin films

We report dielectric and structural properties of Ti and Er co-doped HfO₂ (HfTiErO_x) thin films at different substrate temperatures. The film at 400 °C substrate temperatures has the highest k value of 33, improved flat band voltage of −0.3 V, small hysteresis voltage and the significant interface-state density, which shows better dielectric properties for new high-k microstructure. XPS and XRD results reveal that Hf-Ti-Er-O bond may exist in addition with Hf-O, Hf-Er-O and Hf-Ti-O bonds, while the change in chemical structure and degradation of crystallization quality of HfO₂ thin films are directly related to Ti and Er co-doping.     

Compositional, structural and electronic characteristics of HfO2 and HfSiO dielectrics prepared by radio frequency magnetron sputtering

HfO₂ and HfSiO films were prepared on Si substrates by using radio frequency magnetron sputtering (RFMS). Compositional, structural and electronic properties of the two films were investigated completely. X-ray photoelectron spectroscopy (XPS) spectra showed that the atom ratio of Hf to O was about 1:2 in the HfO₂ film and the chemical composition of the HfSiO film was Hf₃₇Si₇O₅₆. Grazing incidence X-ray diffraction (GI-XRD) patterns indicated crystallization in the HfO₂ film after 400 °C annealing, but there is no detectable crystallization in the HfSiO film after 800 °C annealing. C-V measurements indicated that the dielectric constants for the HfO₂ and HfSiO film were 20.3 and 17.3, respectively. The fixed charge densities were found to be 6.0 × 10¹² cm⁻² for the HfO₂ film and 3.7 × 10¹² cm⁻² for the HfSiO film. I-V characteristics showed that the average leakage current densities were 2.4 μA/cm² for the HfO₂ film and 0.2 μA/cm² for the HfSiO film at the gate bias of 1 V.     

Hysteresis-free HfO2 film grown by atomic layer deposition at low temperature

Hysteresis-free hafnium oxide films were fabricated by atomic layer deposition at 90 °C without any post-deposition annealing, and their structures and properties were compared with films deposited at 150 °C and 250 °C. The refractivity, bandgap, dielectric constant and leakage current density all increase with deposition temperature, while the growth rate and breakdown field decrease. All films are amorphous with roughly the same composition. Although the thin films deposited at the above-mentioned temperatures all show negligible hysteresis, only the 90 °C-deposited films remain hysteresis-free when the film thickness increases. The 90 °C-deposited films remain hysteresis-free after annealing at 300 °C. The hysteresis in films deposited at high temperatures increases with deposition temperature. Evidences show such hysteresis originates in the HfO₂ film instead of the interface. Based on a careful structure analysis, middle-range order is suggested to influence the trap density in the films. HfO₂ films deposited at low temperature with negligible hysteresis and excellent electrical properties have great potential for the fabrication and integration of devices based on non-silicon channel materials and in applications as tunneling and blocking layers in memory devices.     

Thickness dependence of high-k materials on the characteristics of MAHONOS structured charge trap flash memory

The electrical characteristics of tunnel barrier engineered charge trap flash (TBE-CTF) memory of MAHONOS (Metal/Al₂O₃/HfO₂/SiO₂/Si₃N₄/SiO₂/Si) structure were investigated. The stack of SiO₂/Si₃N₄/SiO₂ films were used as engineered tunnel barrier, HfO₂ and Al₂O₃ films were used as charge trap layer and blocking oxide layer, respectively. For comparison, the electrical characteristics of MONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si), MONONOS (Metal/SiO₂/Si₃N₄/SiO₂/Si₃N₄/SiO₂/Si), and MAHOS (Metal/Al₂O₃/HfO₂/SiO₂/Si) were also evaluated. The energy band diagram was designed by using the quantum-mechanical tunnel model (QM) and then the CTF memory devices were fabricated. As a result, the optimized thickness combination of MAHONOS structure was confirmed. The tunnel barrier engineered MAHONOS CTF memory showed a considerable enhancement of program/erase (P/E) speeds, retention time and endurance characteristics.     

Effects of physical growth conditions on the structural and optical properties of sputtered grown thin HfO2 films

HfO₂ thin films were prepared by reactive DC magnetron sputtering technique on (100) p-Si substrate. The effects of O₂/Ar ratio, substrate temperature, sputtering power on the structural properties of HfO₂ grown films were studied by Spectroscopic Ellipsometer (SE), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrum, and X-ray photoelectron spectroscopy (XPS) depth profiling techniques. The results show that the formation of a SiO_x suboxide layer at the HfO₂/Si interface is unavoidable. The HfO₂ thickness and suboxide formation are highly affected by the growth parameters such as sputtering power, O₂/Ar gas ratio during sputtering, and substrate temperature. XRD spectra show that the deposited films have (111) monoclinic phase of HfO₂, which is also supported by FTIR spectra. XPS depth profiling spectra shows that highly reactive sputtered Hf atoms consume some of the oxygen atoms from the underlying SiO₂ to form HfO₂, leaving Si-Si bonds behind.     

Electrical properties of alumina films grown on Si at low temperature using catalytic CVD

The electrical properties of alumina films formed at substrate temperatures as low as 27 °C using tri-methyl aluminum (TMA) and molecular oxygen (O₂) by catalytic chemical vapor deposition (Cat-CVD) have been investigated by capacitance-voltage (C-V), current-voltage (I-V) measurements and X-ray photoelectron spectroscopy (XPS). Substrate temperature dependence of dielectric constant and leakage current of the films has been explained on the basis of deficiency in oxygen. Interface trapping density of the order of 10⁹ ev^− 1cm^− 2 has been obtained. Angle resolved XPS measurements have revealed that the direct bonding of alumina and Si was realized with very small interface trapping density.     

Structural and electrical properties of HfO2/Dy2O3 gate stacks on Ge substrates

In the present work we report on the structural and electrical properties of metal-oxide-semiconductor (MOS) devices with HfO₂/Dy₂O₃ gate stack dielectrics, deposited by molecular beam deposition on p-type germanium (Ge) substrates. Structural characterization by means of high-resolution Transmission Electron Microscopy (TEM) and X-ray diffraction measurements demonstrate the nanocrystalline nature of the films. Moreover, the interpretation of the X-ray reflectivity measurements reveals the spontaneous growth of an ultrathin germanium oxide interfacial layer which was also confirmed by TEM. Subsequent electrical characterization measurements on Pt/HfO₂/Dy₂O₃/p-Ge MOS diodes show that a combination of a thin Dy₂O₃ buffer layer with a thicker HfO₂ on top can give very good results, such as equivalent oxide thickness values as low as 1.9 nm, low density of interfacial defects (2-5 × 10¹² eV^− 1 cm^− 2) and leakage currents with typical current density values around 15 nA/cm² at V_g = V_FB − 1V.     

Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.     

The influence of lanthanum doping position in ultra-thin HfO2 films for high-k gate dielectrics

Lanthanum dopant positioning at HfO₂ ultra-thin films was achieved by the co-sputtering method. The physical properties of graded doping HfO₂/HfLaO/p-Si and HfLaO/HfO₂/p-Si structures after 850 °C postannealing were compared. The thickness of the monolayer was analyzed by X-ray reflectivity and confirmed by the multiple beam interference model. The HfO₂ and silicate phases were characterized by X-ray diffraction patterns. It is found that crystallization depends on the ratio of stacked film thicknesses, and the HfLaO/HfO₂/Si structure has more silicate formation at the interface than the HfO₂/HfLaO/Si structure. Metal-insulator-semiconductor capacitors were fabricated. The electrical properties including leakage current, conduction mechanism, flatband voltage shift, and barrier height were studied.     

Rare-earth substituted HfO2 thin films grown by metalorganic chemical vapor deposition

Thin films of HfGdO_x and HfDyO_x were deposited by metalorganic chemical vapor deposition (MOCVD) utilizing guanidinate precursors for Hf, Gd and Dy. The close match in the thermal properties of the precursors enabled the MOCVD of rare-earth (RE) substituted HfO₂ over a wide temperature window. Film deposition was carried out in the temperature range 300-700 °C in the presence of oxygen on Si(100) substrates. HfGdO_x films were analyzed in detail for their structure, composition and morphology using X-ray diffraction, Rutherford backscattering spectrometry, proton induced X-ray emission, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrical properties of HfGdO_x in terms of capacitance-voltage and current-voltage characteristics of metal-insulator-semiconductor device structures were evaluated.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_siH4 = 0.8 Torr, the resistivity gradually increased, but for P_siH4 = 1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Interconnect and contact for nanoelectronics: Metallic TaSi2 nanowires

TaSi₂ nanowires have been synthesized on Si substrate by annealing FeSi₂ thin film and NiSi₂ films at 950 °C in an ambient containing Ta vapor whose length would be grown up to 13 μm. The metallic TaSi₂ nanowires exhibit excellent electrical properties with remarkable high failure current density of 3 × 10⁸ A cm^− 2. In addition, the growth mechanism is addressed in detail, The TaSi₂ nanowires are formed in three steps: segregation of Si atoms from the FeSi₂ thin film and NiSi₂ films underlayer to form Si base, growth of TaSi₂ nanodots on Si base, and elongation of TaSi₂ nanowire along the growth direction. This simple approach promises future applications in nanoelectronics and nano-optoelectronics.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_SiH4=0.8 Torr, the resistivity gradually increased, but for P_SiH4=1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Overview about the optical properties and mechanical stress of different dielectric thin films produced by reactive-low-voltage-ion-plating

Thin films of Ta₂O₅, Nb₂O₅, and HfO₂ were deposited by reactive-low-voltage-ion-plating (RLVIP) on unheated glass and silicon substrates. The film thickness was about 200 nm. Optical properties as well as mechanical film stress of these layers were investigated in dependence of various deposition parameters, i.e. arc current and oxygen partial pressure. For an arc current in the range between 40 and 50 A and an oxygen partial pressure of at least 11 · 10^− 4 mbar good results were obtained. The refractive index and film thickness were calculated from spectrophotometric transmission data using the Swanepoel theory. For example at 550 nm wavelength the refractive index for thin RLVIP-Nb₂O₅-films was found to be n₅₅₀ = 2.40. The optical absorption was obtained by photo-thermal deflection spectrometry. For the investigated materials absorption coefficients in the range of k = 5 · 10^− 4 at 515 nm wavelength were measured. The mechanical film stress was determined by measuring the difference in bending of silicon substrates before and after the deposition process. For dense films, i.e. no water vapour sorption on atmosphere, the mechanical film stress was always compressive with values of some hundred MPa. In case of films deposited with higher arc currents (I_arc > 60A) and lower oxygen pressure (< 15 · 10^− 4 mbar) the influence of a post deposition heat treatment at 350 °C for 4 h on air was also investigated. For these films the properties could clearly be improved by such treatment. However, by using lower arc currents and higher oxygen partial pressure during the ion plating process, immediately dense and environmental stable films with good optical as well as mechanical properties could be achieved without post deposition heat treatment. All the results obtained will be presented in graphs and diagrams.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Characterization of polycrystalline SiC films grown by HW-CVD using silicon tetrafluoride

SiC films were synthesized by hot-wire chemical vapor deposition using a tungsten filament and a gas mixture of SiF₄ and CH₄. The etching of the substrate instead of the film growth occurred on the samples prepared using only source gases without H₂ dilution. The atomic or molecular hydrogen was believed to control the density of radicals containing F in a gas phase or on a growth surface. Polycrystalline 3C-SiC(111) films were successfully obtained at substrate temperatures lower than 500 °C by using H₂ dilution. The growth mode limited by source-gas supply was found to be important to obtain polycrystalline SiC films. The SiC film grown at higher deposition pressure was amorphous and contained no Si-H_x bonds but 6% fluorine. In SiF₄/CH₄/H₂ system, the radicals containing F are considered to play very important roles in the reactions both on a growth surface and in a gas-phase.     

HfO2 gate insulator formed by atomic layer deposition for thin-film-transistors

We have investigated the effects of annealing temperature on the physical and electrical properties of the HfO₂ film deposited by an atomic layer deposition (ALD) method for high-k gate oxides in thin-film-transistors (TFTs). The ALD deposition of HfO₂ directly on the Si substrate at 300 °C results in the formation of thin HfSi_xO_y interfacial layer between Si and HfO₂. The subsequent low temperature N₂-annealing of HfO₂ films (i.e., 300 °C) using a rapid thermal processor (RTP) improves the overall electrical characteristics of HfSi_xO_y-HfO₂ films. Based on the current work, we suggest that HfO₂ film deposited by the ALD method is suitable for high-k gate oxides in TFTs, which have to be fabricated at low temperature.     

Effect of the oxygen fraction on the structure and optical properties of HfOxNy thin films

The main purpose of this work was to prepare hafnium oxynitride (HfO_xN_y) thin films. HfO_xN_y thin films were deposited by radio frequency reactive magnetron sputtering from a pure Hf target onto Quartz and ZnS substrates at room temperature. The depositions were carried out under an oxygen-nitrogen-argon atmosphere by varying the flow rate of the reactive gases (oxygen/nitrogen ratio). The variation of the flow rate of the reactive gases changed the structure and properties of the films. Glancing incidence X-ray diffraction (GIXRD) was used to study the structural changes of as-deposited films; a new crystalline hafnium oxynitride phase was formed in a region of oxygen/nitrogen ratio. Cross-section of the films observed by SEM revealed that the films grew with a columnar-type structure, and surface observation with AFM showed values of surface roughness changed with the flow rate of the reactive gases, higher oxygen fraction had lower surface roughness than lower oxygen fraction. Visible spectra, infrared spectra, refractive index, absorption coefficient also changed with the variation of the oxygen fraction.     

Study of electrical and micro-structural properties of high-κ gate dielectric stacks deposited using pulse laser deposition for MOS capacitor applications

The electrical properties of hafnium oxide (HfO₂) gate dielectric as a metal–oxide–semiconductor (MOS) capacitor structure deposited using pulse laser deposition (PLD) technique at optimum substrate temperatures in an oxygen ambient gas are investigated. The film thickness and microstructure are examined using ellipsometer and atomic force microscope (AFM), respectively to see the effect of substrate temperatures on the device properties. The electrical J–V, C–V characteristics of the dielectric films are investigated employing Al–HfO₂–Si MOS capacitor structure. The important parameters like leakage current density, flat-band voltage (V_fb) and oxide-charge density (Q_ox) for MOS capacitors are extracted and investigated for optimum substrate temperature. Further, electrical studies of these MOS capacitors have been carried out by incorporating La₂O₃ into HfO₂ to fabricate HfO₂/La₂O₃ dielectric stacks at an optimized substrate temperature of 800 °C using a PLD deposition technique under oxygen ambient. These Al–HfO₂–La₂O₃–Si dielectric stacks MOS capacitor structure are found to possess better electrical properties than that of HfO₂ based MOS capacitors using the PLD deposition technique.