Comparative study of pulsed laser deposited HfO2 and Hf–aluminate films for high-k gate dielectric applications

The thermal stability and the electrical properties of HfO₂ and Hf–aluminate films prepared by the pulsed laser deposition technique have been investigated by X-ray diffraction, differential thermal analysis, capacitance–voltage correlation, leakage-current measurements and high-resolution transmission electron microscopy observation, respectively. A crystallization transformation from HfO₂ amorphous phase to polycrystalline monoclinic structure occurs at about 500 °C. In contrast, the amorphous structure of Hf–aluminate films remains stable at higher temperatures up to 900 °C. Rapid thermal annealing at 1000 °C for 3 min leads to a phase separation in Hf–aluminate films. Tetragonal HfO₂(111) is predominant, and Al₂O₃ separates from Hf–aluminate and is still in the amorphous state. The dielectric constant of amorphous HfO₂ and Hf–aluminate films was determined to be about 26 and 16.6, respectively, by measuring a Pt/dielectric film/Pt capacitor structure. A very small equivalent oxide thickness (EOT) value of 0.74 nm for a 3-nm physical thickness Hf–aluminate film on a n-Si substrate with a leakage current of 0.17 A/cm² at 1-V gate voltage was obtained. The interface at Hf–aluminate/Si is atomically sharp, while a thick interface layer exists between the HfO₂ film and the Si substrate, which makes it difficult to obtain an EOT of less than 1 nm. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Characteristics of SrBi2Ta2O9 ferroelectric films on Si using LaAlO3 thin film as an insulator

Metal–ferroelectric–insulator–semiconductor structures using LaAlO₃ (LAO) layers as an insulating barrier have been investigated. LAO films were deposited on n-Si substrates by low-pressure metalorganic chemical vapor deposition (MOCVD). SrBi₂Ta₂O₉ (SBT) films were prepared as ferroelectric layers at a low processing temperature of 650 °C by a metalorganic decomposition method. The MOCVD-derived LAO buffer layer shows an amorphous structure, relatively high dielectric constant, and good electrical properties. Au/SBT/LAO/n-Si exhibits a larger counterclockwise C–V memory window of 3.7 V and a lower leakage-current density of 2.5×10^-8 A/cm² at an applied voltage of 10 V. It has been confirmed that the hysteresis loop is caused by ferroelectricity. The Auger electron spectrometry depth profile indicates that the introduction of the LAO buffer layer prevents the interfacial diffusion between SBT and the Si substrate effectively and improves the interface quality. PACS 77.84.Dy; 81.15.Fg     

Growth behavior of high k LaAlO3 films on Si by metalorganic chemical vapor deposition for alternative gate dielectric application

LaAlO₃ (LAO) is explored in this work to replace SiO₂ as the gate dielectric material in metal–oxide–semiconductor field effect transistor. Amorphous LAO gate dielectric films were deposited on Si (0 0 1) substrates by low pressure metalorganic chemical vapor deposition using La(dpm)₃ and Al(acac)₃ sources. The effect of processing parameters such as deposition temperature and precursor vapor flux on growth, structure, morphology, and composition of LAO films has been investigated by various analytical methods deeply. The film growth mechanism on Si is reaction limiting instead of mass transport control. The reaction is thermally activated with activation energy of 37 kJ/mol. In the initial growth stage, Al element is deficient due to higher nucleation barrier on Si. The LAO films show a smooth surface and good thermal stability and remain amorphous up to a high temperature of 850 °C. The electrical properties of amorphous LAO ultrathin films on Si have also been evaluated, indicating LAO is suitable for high k gate dielectric applications.     

Interfacial structure and electrical properties of LaAlO3 gate dielectric films on Si by metalorganic chemical vapor deposition

LaAlO₃ (LAO) gate dielectric films were deposited on Si substrates by low-pressure metalorganic chemical vapor deposition. The interfacial structure and composition distribution were investigated by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectroscopy (SIMS), and Auger-electron spectroscopy (AES). HRTEM confirms that there exists an interfacial layer between LAO and Si in most samples. AES, SIMS, and XPS analyses indicate that the interfacial layer is compositionally graded La–Al silicate and the Al element is severely deficient close to the Si surface. Electrical properties of LAO films were evaluated. No evident difference in electrical properties between samples with and without native SiO₂ layers was observed. The electrical properties are discussed in terms of LAO growth mechanisms, in relation to the interfacial structure. PACS 73.40.Qv; 81.15.Gh; 77.55.+f; 68.35.-p     

Study of interfacial oxide layer of LaAlO3 gate dielectrics on Si for metal–insulator–semiconductor devices

Lanthanum aluminate (LAO) thin films were deposited on silicon by pulsed-laser deposition. It was found that oxygen partial pressure played an essential role in the formation of an interfacial layer. The films deposited in nitrogen at a pressure of 20 Pa had no interfacial layer. However, an interfacial layer was observed in the films deposited in 1×10^-2 Pa atmosphere. According to the thickness of the LAO film and interfacial layer and the measured capacitance, it could be deduced that the interfacial layer was not pure SiO₂. Auger electron spectroscopy, secondary ion mass spectroscopy and X-ray photoelectron spectroscopy depth analyses indicated that the interfacial layer was La–Al–silicate rather than pure silicon oxide and that the La and Al concentrations in the interfacial layer had gradients from the LAO layer to the substrate. PACS 79.61.Jv; 77.55.+f; 81.15.Gh     

Superior electromechanical performance over PZT, in lead zinc niobate (PZN)–lead zirconium titanate (PZT) thin films

Strongly oriented thin films of lead zinc niobate (PZN)–lead zirconium titanate (PZT) with (La,Sr)CoO₃ lower electrodes were grown on MgO {001} substrates by pulsed laser deposition. The films were perovskite-dominated with strong in-plane and out-of-plane orientations. Room-temperature functional characterisation indicated that the films were ferroelectric, with dielectric constant ∼550 and loss tangent ∼0.08 at 1 kHz. The crystallographic strain, as a function of applied dc field, was monitored by in situ X-ray diffraction. The maximum electric-field-induced crystallographic strain (∼0.22%) was comparable to that observed in bulk, but at significantly greater field (∼150 kV cm^-1). The effective d₃₃ value obtained from the crystallographic strain data was around 150 pm V^-1, which is high for ferroelectric thin films 400 nm in thickness. The local polarisation-switching properties of the films were investigated using a piezo-response atomic force microscope. Domain maps for a 5×5 μm² region of material were recorded as a function of dc bias, and confirmed the ferroelectric switching behaviour. PACS 81.05.Je; 81.40.Vw; 68.37.Lp     

Effect of deposition temperature on orientation and electrical properties of (K0.5Na0.5)NbO3 thin films by pulsed laser deposition

Lead-free ferroelectric K_0.5Na_0.5NbO₃ (KNN) thin films have been prepared on Pt/TiO₂/SiO₂/Si substrates by pulsed laser deposition process. The structures, crystal orientations and electrical properties of thin films have been investigated as a function of deposition temperature from 680 °C to 760 °C. It is found that the deposition temperature plays an important role in the structures, crystal orientations and electrical properties of thin films. The crystallization of thin films improves with increasing deposition temperature. The thin film deposited at 760 °C exhibits strong (0 0 1) preferential orientation, large dielectric constant of 930 and the remnant polarization of 8.54 μC/cm².     

Effects of texture on the dielectric properties of Ba(Zr0.2Ti0.8)O3 thin films prepared by pulsed laser deposition

Ba(Zr_0.2Ti_0.8)O₃ (BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a pulsed laser deposition process. The BZT thin films directly grown on annealed and un-annealed Pt/Ti/SiO₂/Si substrates exhibited random and high (100) orientations, respectively. The dielectric constant of a 400-nm-thick BZT film with (100) orientation was 331, which was higher than that of a BZT film with random orientation (∼236). This result is attributed to the fact that the polar axis of the (100)-oriented films was more tilted away from the normal to the film surface than that of the randomly oriented films. Also, the tunabilities of BZT thin films with random and (100) orientations were ∼50% and ∼59% at an applied field of 400 kV/cm, respectively. Improved tunability has been attributed to the (100) texture of the film leading to an enhancement of the in-plane-oriented polar axis. PACS 77.22.-d; 77.55.+f; 77.80.-e; 77.84.-s     

Structure Stability of LaAlO3 Thin Films on Si Substrates

A series of amorphous and single-crystalline LaAlO3 （LAO） thin films are fabricated by laser molecular-beam epitaxy technique on Si substrates under various conditions of deposition. The structure stability of the LAO films annealed in high temperature and various ambients is studied by x-ray diffraction as well as high-resolution transmission electron microscopy. The results show that the epitaxial LAO films have very good stability, and the structures of amorphous LAO thin films depend strongly on the conditions of deposition and post-annealing. The results reveal that the formation of LAO composition during the deposition is very important for the structure stability of LAO thin films.     

Thermal stability and electrical properties of Zr silicate films for high-k gate-dielectric applications, as prepared by pulsed laser deposition

Zirconium silicate films with high thermal stability and good electrical properties have been prepared on n-Si(100) substrates and commercially available Pt-coated Si substrates to fabricate metal–insulator–metal (MIM) structures by the pulsed laser deposition (PLD) technique using a Zr_0.69Si_0.31O_2- ceramic target. Rapid thermal annealing (RTA) in N₂ was performed. X-ray diffraction indicated that the films annealed at 800 °C remained amorphous. Differential thermal analysis revealed that amorphous Zr silicate crystallized at 830 °C. X-ray photoelectron spectroscopy showed that RTA annealing of Zr silicate films at 900 °C led to phase separation. The dielectric constant has been determined to be about 18.6 at 1 MHz by measuring the Pt/Zr silicate/Pt MIM structure. The equivalent oxide thicknesses (EOTs) and the leakage-current densities of films with 6-nm physical thickness deposited in O₂ and N₂ ambient were investigated. An EOT of 1.65 nm and a leakage current of 31.4 mA/cm² at 1-V gate voltage for the films prepared in N₂ and RTA annealed in N₂ at 800 °C were obtained. An amorphous Zr-rich Zr silicate film fabricated by PLD looks to be a promising candidate for future high-k gate-dielectric applications. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Pulsed laser deposition of Er:BaTiO3 for planar waveguides

Laser radiation is used for the deposition of dielectric erbium doped BaTiO₃ thin films for photonic applications. Pulsed laser deposition with KrF excimer laser radiation (wavelength 248 nm, pulse duration 20 ns) is used to grow dense, transparent, amorphous, poly-crystalline and single crystalline erbium doped BaTiO₃ thin films. Visible emission due to up-conversion luminescence (wavelength 528 nm and 548 nm) under excitation with diode laser radiation at a wavelength of 970–985 nm is investigated as a function of the erbium concentration of 1–20 mol% and structural film properties. PACS 81.15.Fg; 42.55.Wd; 68.55; 78.55.Hx     

Surface characterisation and interface studies of high-k materials by XPS and TOF-SIMS

High-k dielectric LaAlO₃ (LAO) films on Si(100) were studied by TOF-SIMS and XPS to look for diffusion processes during deposition and additional thermal treatment and for the formation and composition of possible interfacial layers. The measurements reveal the existence of SiO₂ at the LAO/Si interface. Thermal treatment strengthens this effect indicating a segregation of Si. However, thin LAO layers show no interfacial SiO₂ but the formation of a La-Al-Si-O compound. In addition, Pt diffusion from the top coating into the LAO layers occurs. Within the LAO layer C is the most abundant contamination (10²¹ at/cm³). Its relatively high concentration could influence electric characteristics. XPS shows that CO₃²⁻ is intrinsic to the LAO layer and is due to the adsorption of CO₂ of the residual gas in the deposition chamber.     

Room-temperature pulsed laser deposition and dielectric properties of amorphous Bi3.95Er0.05Ti3O12 thin films on conductive substrates

Bi_3.95Er_0.05Ti₃O₁₂ (BErT) thin films were prepared on Pt/Ti/SiO₂/Si and indium-tin-oxide (ITO)-coated glass substrates at room temperature by pulsed laser deposition. These thin films were amorphous with uniform thickness. Excellent dielectric characteristics have been confirmed. The amorphous BErT thin films deposited on the Pt/Ti/SiO₂/Si and ITO-coated glass substrates exhibited almost the same dielectric constant of 52 with a low dielectric loss of less than 0.02 at 1 kHz. Meanwhile, the dielectric properties of the thin films had an excellent bias voltage stability and thermal stability. The amorphous BErT thin films might have potential applications in microelectronic and optoelectronic devices.     

Ferroelectric properties of Nd-substituted bismuth titanate thin films processed at low temperature

Nd-substituted bismuth titanate Bi_3.54Nd_0.46Ti₃O₁₂ (BNT) thin films were prepared on (111)Pt/Ti/SiO₂/Si substrates by a sol–gel method. The BNT thin films processed at a low annealing temperature of ∼600 °C showed good ferroelectric properties. The randomly oriented BNT single phases and the improved ferroelectric properties were confirmed by X-ray diffraction and polarization–electric field hysteresis loops, respectively. The remanent polarization of the BNT thin films is 64 μC/cm², which is larger than that of Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films. After 10¹⁰ read/write switching cycles, the effective non-volatile charges showed no polarization fatigue. Regardless of the low annealing temperature of 600 °C, the BNT thin films had good ferroelectric properties with high remanent polarizations and strong fatigue resistances. PACS 77.84.Dy     

Improving the dielectric constant of Al2O3 by cerium substitution for high-k MIM applications

Process compatible high-k dielectric thin films are one of the key solutions to develop high performance metal–insulator–metal (MIM) structures for future microelectronic devices. Engineered cerium–aluminate (Ce_xAl_2–xO₃) thin films were deposited on titanium nitride metal electrodes by electron-beam co-evaporation of ceria and alumina in a molecular beam deposition chamber. X-ray photoelectron spectroscopy clearly reveals that Ce cations can be stabilized in the 3+ valence state in Ce_xAl_2–xO₃ up to x = 0.7 by accommodation in the alumina host matrix. Higher Ce content was observed to result in cerium dioxide segregation in cerium aluminate matrix, probably due to the chemical tendency of Ce cations to exist rather in the 4+ than in the 3+ state. Electrical characterization of the X-ray amorphous Ce_0.7Al_1.3O₃ films reveals a dielectric constant value of about 11 and leakage current lower than 10^?4 A/cm². No parasitic low-k interface formation between the high-k Ce_0.7Al_1.3O₃ film and the TiN metal electrode is detected.     

Development of a novel high speed (electron-mobility) epi-n-ZnO thin films by L-MBE for III–V opto-electronic devices

Intrinsic epitaxial zinc oxide (epi-ZnO) thin films were grown by laser-molecular beam epitaxy (L-MBE), i.e., pulsed laser deposition (PLD) technique using Johnson Matthey “specpure”-grade ZnO pellets. The effects of substrate temperatures on ZnO thin film growth, electrical conductivity (σ), mobility (μ) and carrier concentration (n) were studied. As well as the feasibility of developing high quality conducting oxide thin films was also studied simultaneously. The highest conductivity was found for optimized epi-ZnO thin films is σ=0.06×10³ ohm⁻¹ cm⁻¹ (n-type) (which is almost at the edge of semiconductivity range), carrier density n=0.316×10¹⁹ cm⁻³ and mobility μ=98 cm²/V s. The electrical studies further confirmed the semiconductor characteristics of epi-n-ZnO thin films. The relationship between the optical and electrical properties were also graphically enumerated. The electrical parameter values for the films were calculated, graphically enumerated and tabulated. As a novelty point of view, we have concluded that without doping and annealing, we have obtained optimum electrical conductivity with high optical transparency (95%) for as deposited ZnO thin films using PLD. Also, this is the first time that we have applied PLD made ZnO thin films to iso-, hetero-semiconductor–insulator–semiconductor (SIS) type solar cells as transparent conducting oxide (TCO) window layer. We hope that surely these data be helpful either as a scientific or technical basis in the semiconductor processing.     

Characteristics of sandwich-structured Al2O3/HfO2/Al2O3 gate dielectric films on ultra-thin silicon-on-insulator substrates

Sandwich-structure Al₂O₃/HfO₂/Al₂O₃ gate dielectric films were grown on ultra-thin silicon-on-insulator (SOI) substrates by vacuum electron beam evaporation (EB-PVD) method. AFM and TEM observations showed that the films remained amorphous even after post-annealing treatment at 950 °C with smooth surface and clean silicon interface. EDX- and XPS-analysis results revealed no silicate or silicide at the silicon interface. The equivalent oxide thickness was 3 nm and the dielectric constant was around 7.2, as determined by electrical measurements. A fixed charge density of 3 × 10¹⁰ cm⁻² and a leakage current of 5 × 10⁻⁷A/cm² at 2 V gate bias were achieved for Au/gate stack /Si/SiO₂/Si/Au MIS capacitors. Post-annealing treatment was found to effectively reduce trap density, but increase in annealing temperature did not made any significant difference in the electrical performance.     

Structure and dielectric properties of ultra-thin ZrO<Subscript>2</Subscript> films for high-<Emphasis Type="Italic">k</Emphasis> gate dielectric application prepared by pulsed laser deposition

ZrO₂ thin films have been prepared on Pt-coated silicon substrates and directly on n-Si(100) substrates by the pulsed laser deposition (PLD) technique using a ZrO₂ ceramic target under different deposition conditions. X-ray diffraction showed that the films prepared at 400 °C in 20 Pa oxygen ambient remained amorphous. Differential thermal analysis was carried out to study the crystallization behavior of ZrO₂. The dielectric constant of ZrO₂ was determined to be around 24 by measuring a Pt/ZrO₂/Pt capacitor structure. Sputtering depth profile X-ray photoelectron spectroscopy was used to investigate the interfacial characteristics of ZrO₂/n-Si stacks. A Zr silicate interfacial layer was formed between the ZrO₂ layer and the silicon substrate. The equivalent oxide thickness (EOT) and leakage current densities of the films with 6.6 nm physical thickness post-annealed in O₂ and N₂ ambient were investigated. An EOT of 1.65 nm with a leakage current of 36.2 mA/cm² at 1 V gate voltage for the film post-annealed in N₂ has been obtained. ZrO₂ thin films prepared by PLD have acceptable structure and dielectric properties required by a candidate material of high-k gate dielectrics. PACS 77.55.+f; 81.15.Fg; 73.40.Qv     

Pulsed laser deposition of PZT/Pt composite thin films with high dielectric constants

PbZr_0.53Ti_0.47O₃ (PZT) thin films containing nanoparticles of Pt (3–10 nm) were produced using pulsed laser deposition (PLD). The Pt content can be tuned by varying the energy density of the laser beam. Phase and microstructure analysis of the thin films was performed using XRD, SEM, TEM and AFM. The electrical properties were investigated by C–V and I–V measurements. The effective dielectric constant of the composite films increased substantially through the Pt dispersion. These films are promising candidates, for instance, for high-density dynamic random access memory (DRAM) devices. PACS 77.22.Ch; 77.84.Lf; 81.15.Fg     

Low-temperature laser processes for synthesizing (100)-textured Pb(Zr,Ti)O3 thin films on Si substrate

High-performance Pb(Zr,Ti)O₃, PZT, thin films were synthesized on Si substrates by using low-temperature laser-assisted processes, which combine pulsed laser deposition (PLD), laser lift-off (LLO) and laser-annealing (LA) processes. The PZT films were first grown on sapphire substrates at 400 °C, using Ba(Mg_1/3Ta_2/3)O₃, BMT, as seeding layer, by the PLD process, and were then transferred to Si substrates at room temperature by a LLO transferring process. Utilization of the BMT layer is of critical importance in those processes, since it acted as a nucleation layer for the synthesis of the PZT thin films on the sapphire substrates and, at the same time, served as a sacrificial layer during laser irradiation in the LLO process. After the LLO process, the surfaces of the PZT films were recovered by the LA process for removing the damage induced by the LLO process. A thin BMT (∼30 nm) layer is randomly oriented, resulting in non-textured PZT films with good ferroelectric properties, viz. P_r=20.6 μC/cm² and E_c=126 kV/cm, whereas a thick BMT (∼100 nm) layer is (100) preferentially oriented, leading to (100)-textured PZT films with markedly better ferroelectric properties, viz. P_r=34.4 μC/cm² and E_c=360 kV/cm. PACS 81.15.Fg; 77.84.-s