We review our capacitor technology using (Ba,Sr)TiO3 (BST) as a capacitor dielectric for dynamic random access memory (DRAM) application. Among a number of issues for BST capacitor process integration in DRAM cells, two important technologies are discussed. As an electrode technology, we propose All PErovskite Capacitor (APEC) technology, in which conducting perovskite oxide of SrRuO3 (SRO) is used as capacitor electrodes. For chemical vapor deposition (CVD) of BST, we propose In-situ Multi-Step (IMS) process, which is a sequential repetition of low temperature deposition of ultra thin BST film and crystallization in the same chamber. By using APEC technology and IMS CVD process of BST, we can simultaneously achieve good electrical characteristics (low leakage current and high permittivity) and good step coverage. The combination of APEC technology and IMS CVD process of BST is a promising BST capacitor process technology for future DRAMs.

Recent progress to overcome integration issues related with (Ba,Sr)TiO3 films are presented. Firstly, ternary barrier material, Ti0.7Al0.3N deposited by reactive sputtering is shown to have superior oxidation resistance than TiN through the test using contact string pattern where Pt is deposited as a electrode. Ti0.7Al0.3N barrier is able to keep stable contact resistance below 100Ω even under oxidizing condition where the temperature is 550°C and oxygen partial pressure is 7.6 Torr. If rapid thermal annealing is used, annealing temperature without oxidation of Ti0.7Al0.3N can be increased by about 100°C. Ti0.7Al0.3N is thought to be the promising one which can endure during post-annealing process. Secondly, electroplating technology is employed to fabricate the stack capacitor of Pt that has been known to be very difficult to etch. 500Å-thick Pt is used as a seed layer and very thick Pt is selectively grown on the seed layer by the electroplating. The Pt height can be controlled by changing the electroplating time, so we can make stack Pt over 8000Å. Thirdly, low temperature deposition process for MOCVD BST film is developed. The equivalent oxide thickness of about 3.5Å is obtained on Pt electrode when BST thickness is 150Å. BST film is deposited at 420°C and annealed at 700°C under oxidizing atmosphere. It is suggested that a new two step annealing consisting of high temperature annealing under inert atmosphere and low temperature annealing under oxidizing atmosphere is very effective to achieve the high dielectric constant and low leakage current of BST films at the same time. It is also adequate for preventing the barrier oxidation. BST film with Toxeq. of 5.2Å and low leakage current is obtained by annealing at 650°C under N2 followed by annealing at 550TC under O2. Electrical properties of BST deposited on side-wall of Pt concave capacitor is evaluated. The concave capacitor with about aspect ratio 3 shows the same capacitance and leakage current as the planar capacitor, which implies that BST composition and thickness is uniform on the side-wall. It is concluded that BST films on Pt electrode can be applied to real device.

We have used electrical characterization and secondary ion mass spectroscopy (SIMS) to investigate the influence of hydrogen or deuterium (H/D) on the degradation of the electrical properties of metal/Ba0.7Sr0.3TiO3/metal (M/BSTO/M) thin film capacitors after forming gas annealing (FGA). Leakage and dielectric relaxation currents increase after FGA at temperatures as low as 23C. SIMS profiling shows that at 23C H/D diffuses through thin film metal electrodes and accumulates at electrode interfaces. The location (top or bottom electrode interface) of H/D accumulation is dependent on the type of electrodes and capacitor structure. The resulting asymmetric distribution of H/D leads to large voltage offsets in the C-V characteristic, asymmetric leakage currents, and increased dielectric relaxation currents. Possible mechanisms for increased leakage and relaxation currents after FGA are discussed.

SrTiO3 (STO) thin films were grown by pulsed laser deposition on single crystal STO substrates with a SrRuO3 buffer layer, which also serves as a bottom electrode. Measurements of the low frequency dielectric properties were performed in a parallel plate capacitor configuration for a range of temperatures using different top electrode materials. The contribution to the interfacial potential from Schottky barriers was investigated. In comparison to STO single crystals, thin films have continued dielectric non-linearity above T ∼ 70 K. This complicates conventional Schottky barrier height measurements using C-V curves because both Schottky barriers and dielectric non-linearity result in a decrease in dielectric constant under applied electric fields. However, by using I-V data, difficulties related to field dependence of the dielectric constant may be removed. Barrier height measurements for both metal and oxide electrodes were performed for T > 70 K. Calculated barrier heights from a modified Schottky equation were very low for an oxide electrode, and an order of magnitude higher for a normal metal electrode.

In this work, (Ba0.7Sr0.3)TiO3 thin films on Pt/TiN/Ti/Si substrate were deposited by an RF magnetron co-sputter system at 300°C in an Ar+O2 mixed ambient. In the integration of BST capacitors, the diffusion barrier (TiN) under bottom electrodes is one of the key issues. To obtain a stable and excellent diffusion barrier against inter-diffusion between Pt and Si, as well as against being oxidized during BST deposition, TiN was treated by a rapid thermal annealing (RTA) process. Experimental results indicated that proper RTA treatments resulted in a superior TiN barrier layer. In addition, low substrate temperature during BST deposition suppressed the phenomena of inter-diffusion and barrier oxidation. Furthermore, Pt hillocking, another problem during BST deposition because of high thermal budget, was also solved by reducing substrate temperature during BST deposition. The MIM (Pt/BST/Pt) structure was used in the experiments for electrical properties measurement. High dielectric constant (εr =300), low leakage current (l.5×10−8 A/cm2) under 0.1MV/cm, and 10 year lifetime under 1.6MV/cm were achieved with an Ar+O2 mixed ambient at a low substrate temperature (300°C).

Thin films of (Ba,Sr)TiO3 (BST) have been prepared by rf magnetron reactive sputtering using single alloy target, and in-situ negative DC-bias. Post annealing was applied to the asdeposited films at 620°C for 2 hours in 1 atm oxygen atmosphere. Thin film microstructures and grain sizes were studied and calculated by means of X-ray diffraction, while the film composition was analyzed by Electron Probe X-ray Microanalyzer (EPMA). The dielectric constant of the films was also studied. As the applied DC-bias increased, the dielectric constant increased from 176 to 912, the x-ray diffraction patterns became more intense and narrower, and the (Ba+Sr)/Ti molar ratio increased from 0.70 to 0.83. In-situ DC-bias was observed to be a feasible fabrication process to increase the grain size and relative permittivity of sputtered BST films.

High dielectric constant barium strontium titanium oxide (BST) thin films have been deposited on Ni/TiN/Si by photo-assisted metal organic chemical vapor deposition (PhAMOCVD). Planar capacitors based on the Ni/BST/Ni/TiN/Si heterostructure with BST-layer thickness of 50nm exhibited storage densities of about 30 fF/μm2 and leakage current densities of less than 10–7 A/cm2 under bias below 1.8V at room temperature. Nickel as a bottom electrode in this newly designed capacitor structure, can be easily patterned by reactive ion etching, and satisfies the requirement for integration with silicon.

The possibility that oxygen-containing Pt might be superior to conventional Pt as an electrode for high-epsilon (HE) and ferroelectric (FE) perovskites has led to renewed interest in the family of Pt(O) materials. Here we report on the properties and decomposition behaviors of reactively sputtered Pt(O)-PtOx electrode materials having x in the range 0 to ∼1.4. Phases of Pt(O) identified included <111>-textured cubic Pt (x < 0.2), tetragonal PtO (x ∼ 1), and amorphous platinum oxide a-PtOx (x ∼ 1.4). Film texture, morphology, resistivity, adhesion, and oxygen content were examined before and after annealing in O2 and N2 at temperatures approximating those of HE/FE deposition and processing (400 - 650°C). After annealing at 650 °C for 5 min, all Pt(O) films lost oxygen and showed growth in metallic Pt phases whose orientations were often <200> or <220> rather than the <111> orientation typically produced by physical vapor deposition of the pure metal. Pt(O) films having a PtO-like structure typically showed only surface oxygen loss, with close to original oxygen levels left in the film bulk, suggesting that the oxygen in these films may be retained long enough to have a beneficial effect on HE/FE layers at later stages in processing.

The Metal-Ferroelectric-Metal-Oxide-Silicon (MFMOS) one transistor memory requires a metal electrode directly on top of the thin gate oxide. The gate oxide used in our present MFMOS one transistor memory processing is 30 Å SiO2. Ir has been chosen for the bottom electrode and TaN was used as the barrier layer between the Ir and thin gate oxide. It has been shown from previous studies that a TaN barrier layer can effectively prevent the formation of iridium silicide and can enhance the adhesion between Ir and Si or SiO2 substrates. But it is more important that the TaN itself is stable and will not react with the gate oxide during ferroelectric material deposition, annealing and subsequent processing. In this paper, TaN barriers with different deposition conditions have been deposited on 30 Å gate oxide. 1500 Å Ir was deposited on the TaN barrier layer. Capacitors of Ir/TaN/gate SiO2/Si were defined by dry etching. Series RTP annealing were performed in oxygen from 500 to 650 °C with annealing times from 5 min to 90 min. The capacitor was also annealed in a nitrogen ambient at 1000°C for 10s. C-V and I-V studies were used to characterize the stability of the Ir/TaN/Gate SiO2 structure. It was observed that the Ir/TaN/Gate SiO2 is very stable during the above mentioned annealing conditions. The consumption and further oxidation of the gate oxide is negligible and would depend on the deposition condition of the TaN barrier layer. With optimized deposition conditions, a 220 Å TaN barrier layer can effectively prevent any iridium silicide formation and will not degrade the gate oxide during annealing processing. The interfaces between the TaN and gate SiO2 and between the gate SiO2 and Si substrate can be further improved by forming gas annealing.

In this work, highly (001)pc-oriented thin films of LaNiO3 (LNO) were deposited by DC magnetron sputtering onto Si substrates (pc = pseudocubic indices). The target powder was prepared using a molten salt technique with Na2CO3 as a flux. The final target density was greater than 85% of theoretical density. The best results were obtained when sputtering was carried out at a power of 186 W and a working pressure of 45 mtorr with a gas composition of 50% O2 + 50% Ar. The thickness of the deposited films was proportional to the sputtering time, and the growth rate was 300Å/hour. Highly (001)-oriented thin films of lead zirconate titanate Pb(Zr0.52Ti0.48)O3 (PZT) and Pb[(Mg1/3Nb2/3)0.7Ti0.3]O3 (PMN-PT) were fabricated by a sol-gel method on (001)-textured LNO metallic oxide electrodes. A remanent polarization of 12 μC/cm2 and d31 of -125 pC/N (assuming a Young's modulus of 35 GPa) were measured on the PMN-PT thin films with a thickness of 0.9 μm. This piezoelectric coefficient considerably exceeds that available from PZT films, and depends critically on the film orientation. Changes in the hysteresis loop due to externally applied stress will also be described.

SrRuO3 and CaRuO3 thin films were successfully prepared by metalorganic chemical vapor deposition (MOCVD). Sr(C11H19O2)2(C8H23N5)x – Ru(C11H19O2)3–O2 and Sr(C11H19O2)2(C8H23N5)x. – Ru[(C5H4)(C2H5)]2 - O2 systems, and Ca(C11H19O2)2(C8H23N5)x, – Ru(C11H19O2)3–O2 and Ca(C11 H19O2)2(C8H23N5)x – Ru[(C5H4)(C2H5)]2– O2 systems were used as source materials for SrRuO3 and CaRuO3 thin film preparation, respectively. Sr and Ca source vapors were successfully obtained by bubbling N2 gas including C8H23N5 vapor through liquid sources. Self-composition limiting to keep single phase of SrRuO3 and CaRuO3 was observed under an excess input of the Ru source at 700 – 750 °C for both Ru sources. Epitaxlly grown films with high crystal perfection were grown on various kinds of substrates in this temperature range. Epitaxially grown SrRuO3 film with three kinds of orientation, (100), (110) and (111), were deposited on (100), (110) and (111)SrTiO3 substrates, respectively. By using these films as bottom electrodes, we measured the ferroelectric anisotropy of SrBi2Ta2O9 by preparing (001)- and (116)- oriented films.

An Ir film was grown heteroepitaxially on the epitaxial (100)ZrN film deposited on the (100)Si substrate by sputtering. Further, we obtained a heteroepitaxial (001)PZT film on the epitaxial (100)Ir/(100)ZrN/(100)Si substrate structure by reactive sputtering. The crystallographic relationship was cube-on-cube. The polarization-electric field hysteresis loop of the 300-nm-thick epitaxial PZT film with a top electrode of IrO2 showed a saturated square shape at an ac amplitude of 5V, and the remanent polarization, 2Pr, and coercive field, 2Ec, were 60 μC/cm 2 and 80 kV/cm, respectively. The Pr was not reduced up to 5×1010 switching cycles with a ±10 V bipolar pulse train. The leakage current of the PZT film at +5 V and –5 V was about 8.0× 10−8 and 2.5 ×10−7 A/cm2, respectively.

High density plasma etching of (Ba,Sr)TiO3 (BST) and LaNiO3 (LNO) thin films was performed in two different plasma chemistries, Cl2/Ar and CH4/H2/Ar. While the latter chemistry produced extremely low etch rates (≤ 100 Å-min−1) under all conditions, the Cl2/Ar produced a smooth anisotropic pattern transfer. The etching was still strongly ion-assisted, but maximum removal rates of ∼900 Å min−1 for both materials were achieved with selectivities of ∼16 for BST and ∼7 for LNO over Si. A single layer of thick (∼7 μm) photoresist is an effective mask under these conditions.

The preparation of ferroelectric and high dielectric perovskite materials, which is performed at high temperature (550–750°C) in oxidizing environments, provides strong limitations on the choice of electrode materials which have to be used for integration with semiconductor devices. To minimize interdiffusion and oxidation reactions, a diffusion barrier must be placed between Si substrate and electrode material (Pt, lrO2, RuO2.…). Ti1-xAlxN thin films, deposited by reactive sputtering, are promising materials as electrically conductive layers and robust diffusion barriers. The stability of these films has been investigated at conditions typically used for crystallization of perovskite dielectrics. Films with various Al composition (x=0, 0.1, 0.2 and 0.4) have therefore been annealed by RTA (rapid thermal annealing) in 18O2 at 550–750°C. The concentration depth profiles of both 18O and 27A1 were measured before and after the RTA treatments via the narrow resonances of 18O(p,α)15N at 151 keV (fwhm=100 eV) and 27Al(p,γ)28Si at 992 keV (fwhm=100 eV). Al incorporation in the films reduces oxide growth especially at high annealing temperatures. The Al excitation curves indicate a uniform Al content for as deposited Ti1−xAlxN, and reveal Al diffusion to the surface during oxidation which indicates the formation of an Al rich oxide layer at the Ti1-xAlxN surface.

Platinum film growth using Pt(PF3)4 precursors was investigated. The study focused on three aspects of film growth: conformality, adhesion and selective growth. Pt(PF3)4 deposited pure Pt films over a wide range of temperatures (∼200 to 400 °C). At 200 °C, the step coverage for a via with an aspect ratio of three was poor. Lower growth temperatures showed a significant decrease in the growth rate. In addition, these films had poor adhesion to the substrate as indicated by separation between the Pt and the substrate in cross sectional scanning electron microscopy images. Oxygen addition during Pt film growth from Pt(PF3)4 improved both film conformality and adhesion. With oxygen, the step coverage on the side wall was greater than 90 % The dependence of the film growth rate on oxygen varied with the growth temperature: the growth rate decreased at 200 °C, while it changed slightly at 260 °C when oxygen was added. The substrate effect on the initial growth rate was studied on various substrates. The initial growth rate on metals is much faster than that on other substrates. The growth rate decreased on various substrates in the order of iridium > titanium nitride > barium strontium titanate > silicon nitride > silicon oxide.

Reactive Ion Etching of Ba0.7Sr0.3TiO3 (BST) thin films was studied using a Lam Research Corporation TCP™ 9400SE high density, low pressure plasma reactor. The BST thin films were etched with a variety of reactive gas combinations in a transformer coupled plasma (TCP) by varying etching parameters such as plasma density, DC bias to wafer susceptor, gas pressure, and -flow. The etch process was characterized by measuring the etch rate, etch selectivity to photo resist and SiO2 etch profiles, side wall deposition (fence), and etch product residues. Plasma etching of BST was found to be dominated by physical sputtering. With the chemistries used, the etch products have little or no volatility. Such a process regime is expected to contaminate the wafer with sidewall deposition (fences) and residues, which are both detrimental for further processing and may cause a possible particle problem and a low mean time between cleaning the process tool. The photoresist mask thickness and slope were varied to characterize the relationship between profile and residue. The photoresist mask was sloped using in situ plasma processing. Through optimization of mask and etch parameters, an etch process suitable for integration of BST capacitors into ULSI structures was achieved.

A conductivity difference in a PZT film in a Pt/PZT/Pt capacitor was found by novel charged-up SIMS analyses for the first time. The charged-up SIMS technique was useful for evaluating the conductivity profile in the PZT film. It was found that the conductive region existed in an as-prepared PZT film near the bottom Pt electrode. After hydrogen plasma treatment at 45°C, the conductive region increased in the PZT film near the top electrode. Electrical measurements showed that the leakage current of the capacitor increased after hydrogen treatment. The hydrogen was expected to reduce PZT both at grain boundaries and the electrode-PZT interfaces, and to form the conductive region, which induced an increase in leakage current.

Pt/Bi2SiO5/Si (MIS) and Pt/200nm-Bi4Ti3O12/Pt/30nm-Bi2SiO5/Si (MFMIS:Metal/ Ferroelectric/ Metal/Insulator/Semiconductor) structures were prepared by MOCVD. Oxygen concentration and the Bi/Ti composition ratio determine Bi4Ti3O12 orientation and Bi4Ti3O12 volume in the film, respectively. When the oxygen concentration and the Bi/Ti composition ratio was 33% and 0.65, (001) Bi4Ti3O12 film with the dielectric constant of 40 was obtained. In addition, the capacitance-vs-voltage (C-V) measurement of the Pt/Bi2SiO5/Si structure exhibits normal MIS C-V characteristics. The C-V characteristics of Pt/Bi4Ti3O12/Pt/ Bi2SiO5/Si structure have ferroelectric switching properties with a memory window of about 2.OV Moreover, it is found that the capacitance at zero-bias remains constant for over 24 h.

We discuss some aspects of solid-state chemistry concerning ferroelectric SrBi2Ta2O9, (SBT). Crystal structure analysis by high-resolution neutron diffraction revealed considerable structural distortion in the SBT materials. This distortion, which consists of large atomic displacements of constituent ions, causes large ferroelectric spontaneous polarization. The structural distortion is more pronounced in Sr-deficient-and-Bi-excess material Sr0.8Bi2.2Ta2O9 than in stoichiometric SBT, leading to the larger remanent polarization. The enhanced structural distortion is explained in terms of an “ionic size effect” at the A-cation site. This effect was apparently observed in a series of compounds of ABi2Ta2O9 (A=Ca, Sr, and Ba) with different size A-site cations. On the other hand, analysis of chemical reactions of SBT gave important information on the degradation of the SBT capacitors and on the reaction between the SBT materials and a Pt electrode during device fabrication. The degradation of SBT in an H2- containing reducing atmosphere and its recovery by subsequent annealing in oxygen have been reproduced experimentally by using bulk ceramics and analyzed by thermogravimetric and x-ray- diffraction measurements. SBT decomposes into Bi metal or Bi-Pt alloy in H2 by oxygen dissociation. In the presence of Pt, the SBT degradation and the re-crystallization processes differ from those for SBT alone.

The Bi layered perovskites are promising materials for ferroelectric random access memories (FeRAM's) because of their inherently high resistance to fatigue. Liquid delivery, flash vaporization metalorganic chemical vapor deposition (LD-MOCVD) is an attractive process for these materials, because it offers the ability to produce high quality, conformal films of controlled composition for both high and low density memory applications. We have developed a well-controlled process to deposit Nb-substituted SrBi2Ta2O9 (SBNT) using a mixed alkoxide-β-diketonate precursor Nb(O-i-Pr)4(thd) that is compatible with a previously developed precursor suite for SBT (Sr(thd)2-pmdeta, Bi(thd)3, and Ta(O-i-Pr)4(thd)). The Nb and Ta precursors behave in the same way in the process, making the Nb substitution level in the film identical to that in the precursor solution. In this study, wavelength dispersive x-ray fluorescence has been used to characterize composition and thickness. As-deposited films are smooth, with a surface roughness of 2 nm RMS. After a post-deposition annealing treatment, a high quality layered perovskite crystal structure was obtained. The resultant ferroelectric hysteresis shows a 50% increase in coercive voltage for 28% Nb substitution at the Ta site with the same switchable polarization. In the 28% Nb containing film, imprint was significantly improved compared to SBT films without substitution.