Thermal stability of hafnium silicate dielectric films deposited by a dual source liquid injection MOCVD

The hafnium and silicon precursors, Hf(NMe₂)₄ and Bu^tMe₂SiOH, have been investigated for the MOCVD of high- hafnium silicate, (HfO₂)_1–x –(SiO₂) _x films for gate dielectric applications. Control of the silica concentration in the hafnium silicate can be achieved by varying the relative precursor ratios up to a saturation level of 35–40% SiO₂. The thermal stability of the resulting hafnium silicate films in air has been investigated using medium energy ion scattering. Internal oxidation of the underlying silicon substrate is discernable when the films are annealed in dry air for 15 min over the temperature range 800–1000 °C.     

Preparation and Properties of Thin HfO<Subscript>2</Subscript> Films

HfO₂ layers were grown on silicon by metalorganic chemical vapor deposition using (C₅H₅)₂Hf(CH₃)₂, (C₅H₅)₂Hf(N(C₂H₅)₂)₂, and Hf(dpm)₄ as volatile precursors and were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and IR spectroscopy. The films were shown to consist of monoclinic HfO₂ and to contain hafnium silicide and silicate at the HfO₂/Si interface. The presence of hafnium silicide was attributed to oxygen deficiency produced by argon ion milling. Hafnium silicate was formed as a result of the reaction between hafnium and silicon oxides during annealing. Current-voltage and capacitance-voltage measurements on Al/HfO₂/Si test structures were used to determine the dielectric permittivity and electrical resistivity of the films: ? = 15–20, ρ ～ 10¹⁵ cm.     

Synthesis and characterization of HfO2 and ZrO2 thin films deposited by plasma assisted reactive pulsed laser deposition at low temperature

A plasma assisted reactive pulsed laser deposition process was demonstrated for low-temperature deposition of thin hafnia (HfO₂) and zirconia (ZrO₂) films from metallic hafnium or zirconium with assistance of an oxygen plasma generated by electron cyclotron resonance microwave discharge. The structure and the interface of the deposited films on silicon were characterized by means of Fourier transform infrared spectroscopy, which reveals the monoclinic phases of HfO₂ and ZrO₂ in the films with no interfacial SiO_x layer between the oxide film and the Si substrate. The optical properties of the deposited films were investigated by measuring the refractive indexes and extinction coefficients with the aid of spectroscopic ellipsometry technique. The films deposited on fused silica plates show excellent transparency from the ultraviolet to near infrared with sharp ultraviolet absorption edges corresponding to direct band gap.     

Modelization of hafnium silicate chemical vapor deposition using tetrakis-diethyl-amino-hafnium and tetrakis-dimethyl-amino-silane

The Chemical Vapor Deposition growth mechanism of a hafnium silicate film deposited by means of the co-flow of two precursors, TDEAH (tetrakis-diethyl-amino-hafnium) and 4DMAS (tetrakis-dimethyl-amino-silane), is characterized. Typical growth kinetics demand that the deposition rate increases and the silicon concentration remain stable with increasing reactor pressure. Though the deposition rate follows the expected growth kinetics, the silicon concentration in the silicate does not and exhibits an abnormal increase with increasing reactor pressure. To understand this atypical behavior the formation of pure HfO₂ from TDEAH and pure SiO_x from 4DMAS is first studied. Experimental results show that whereas the HfO₂ deposition is well behaved and fits a diffusion-based model defined by assuming diffusion of TDEAH through a boundary layer, the deposition of SiO_x with 4DMAS requires Hf-O nucleation sites and self-saturates after a single Si―O monolayer is formed. Based on these observations, a model is developed for hafnium silicate formation. The Atomic Layer Deposition like behavior of 4DMAS decomposition results in a deposition rate and film stoichiometry that are weakly sensitive to the 4DMAS partial pressure, and instead are driven by the TDEAH reaction. Since TDEAH operates within a transport-limited regime, the deposition rate is insensitive to substrate temperature, and is only controlled by the TDEAH partial pressure and the gas phase kinematics, rendering the process robust and easily controllable with excellent reproducibility.     

Synthesis and properties of dielectric (HfO2)1 − x (Sc2O3) x films

(HfO₂)_{1 ? x} (Sc₂O₃) _x films have been grown by chemical vapor deposition (CVD) using the volatile complexes hafnium 2,2,6,6-tetramethyl-3,5-heptanedionate (Hf(thd)₄) and scandium 2,2,6,6-tetramethyl-3,5-heptanedionate (Sc(thd)₃) as precursors. The composition and crystal structure of the films containing 1 to 36 at % Sc have been determined. The results demonstrate that, in the composition range 9 to 14 at % scandium, the films are nanocrystalline and consist of an orthorhombic three-component phase, which has not been reported previously. Using Al/(HfO₂)_{1 ? x} (Sc₂O₃) _x /Si test structures, we have determined the dielectric permittivity of the films and the leakage current through the insulator as functions of scandium concentration. The permittivity of the films with the orthorhombic structure reaches k = 42–44, with a leakage current density no higher than ～10^?8 A/cm².     

Formation of gas barrier films by Cat-CVD method using organic silicon compounds

Silicon nitride (SiN_x) and silicon oxynitride (SiO_xN_y) films have been formed by catalytic chemical vapor deposition (Cat-CVD) method using hexamethyldisilazane (HMDS). Addition of NH₃ gas and increase in gas pressure can prevent carbonization of tungsten (W) catalyzer. These SiO_xN_y films have high gas barrier ability compare to the case of SiO_xN_y films using SiH₄ and thus are expected for novel sealing films.     

Physico-chemical, structural and physical properties of hydrogenated silicon oxinitride films elaborated by pulsed radiofrequency discharge

Films prepared by radiofrequency pulsed plasma enhanced chemical vapor deposition from a mixture of silane (SiH₄) and nitrous oxide (N₂O) were studied. Variation of operating conditions (flow rate, deposition temperature ...) resulted in films with chemical compositions changing from hydrogenated silicon oxynitride (SiO_xN_y:H) to silicon oxide (SiO_x:H). Infrared and Rutherford backscattering spectroscopy studies of the as-deposited films revealed different SiO_x arrangements disturbed by Si-N bonds and H-Si ≡ Si_(3 − x)O_x clusters depending on the substrate temperature and the N₂O/SiH₄ ratio. For films obtained using low N₂O/SiH₄ rations and annealed at temperature higher than 1273 K, Raman spectroscopy and microscopy analyses revealed the presence of silicon nanocrystals embedded in a matrix containing Si, O, and N. Spectroscopic ellipsometry revealed the presence of silicon nanocrystals along with two other amorphous phases (SiO_xN_y and SiO₂) in annealed samples. The electrical characteristics of annealed films obtained from capacitance-voltage measurements indicated a stable charge trapping in ultra-thin SiO_xN_y layers. These preliminary results suggest that Si-nc containing silicon oxynitride layers can be potential candidates to be used in the floating gate fabrication of memory devices.     

Nanoindentation stress-strain curves of plasma-enhanced chemical vapor deposited silicon oxide thin films

Plasma-enhanced chemical vapor deposited (PECVD) silicon oxide (SiO_x) thin films have been widely used in Micro/Nano Electro Mechanical Systems to form electrical and mechanical components. In this paper, we explore the use of nanoindentation techniques as a method of measuring equivalent stress-strain curves of the PECVD SiO_x thin films. Four indenter tips with different geometries were adopted in our experiments, enabling us to probe the elastic, elasto-plastic, and fully plastic deformation regimes of the PECVD SiO_x thin films. The initial yielding point (σ_I) and stationary yielding point (σ_II) are separately identified for the as-deposited and annealed PECVD SiO_x thin films, as well as a standard fused quartz sample. Based on the experimental results, a shear transformation zone based amorphous plasticity theory is applied to depict the plastic deformation mechanism in the PECVD SiO_x.     

Effects of niobium content on electrical and mechanical properties of (Na0.85K0.15)0.5Bi0.5Ti(1-x)Nb x O3 thin films

(Na_0.85K_0.15)_0.5Bi_0.5Ti_(1-x)Nb _x O₃ (NKBT-N100x) thin films were deposited on Pt/Ti/SiO₂/Si(100) substrates by metal–organic decomposition method and annealed in oxygen atmosphere at 750 °C. The effects of niobium concentration on the microstructures, ferroelectric, piezoelectric, leakage current and mechanical properties of the NKBT-N100x (x = 0, 0.01, 0.03, 0.05) thin films have been investigated in detail. The NKBT-3N thin film has the largest remnant polarization (7 μC/cm²) and statistically averaged d _33eff (140 pm/V), the smallest leakage current, elasticity modulus (102.0 Gpa), hardness (5.1 Gpa) and residual stress (297.0 Mpa). The evaluation of residual stresses of these thin films will offer useful guidelines of safe working condition for their potential application in microelectromechanical system.     

Conformal growth and characterization of hafnium silicate thin film by MOCVD using HTB (hafnium tertra-tert-butoxide) and TDEAS (tetrakis-diethylamino silane)

Hafnium silicate (HfSi _x O _y ) films were deposited by metal-organic chemical vapor deposition (MOCVD) using hafnium tetra-tert-butoxide [HTB, Hf(OC(CH₃)₃)₄] and tetrakis-diethylamino silane [TDEAS, Si(N(C₂H₅)₂)₄]. The grown Hf-silicate films showed Hf-rich composition and impurity concentrations less than 1 atomic % (below detection limits). Uniformly deposited films with good step-coverage were obtained on hole-patterned SiO₂ substrates. Hafnium silicate films had stable amorphous crystalline structure up to 800 °C annealing and above 900 °C, a tetragonal HfO₂ crystal phase was observed. Dielectric constant (k) of the Hf-silicate films was about 15 and flat band voltage (V _fb) and hysteresis were very low.     

Effect of N2O/SiH4 flow ratios on properties of amorphous silicon oxide thin films deposited by inductively-coupled plasma chemical vapor deposition with application to silicon surface passivation

Silicon oxide (SiO_x) thin films have been deposited at a substrate temperature of 300 °C by inductively-coupled plasma chemical vapor deposition (ICP-CVD) using N₂O/SiH₄ plasma. The effect of N₂O/SiH₄ flow ratios on SiO_x film properties and silicon surface passivation were investigated. Initially, the deposition rate increased up to the N₂O/SiH₄ flow ratio of 2/1, and then decreased with the further increase in N₂O/SiH₄ flow ratio. Silicon oxide films with refractive indices of 1.47-2.64 and high optical band-gap values (>3.3 eV) were obtained by varying the nitrous oxide to silane gas ratios. The measured density of the interface states for films was found to have minimum value of 4.3 × 10¹¹ eV⁻¹ cm⁻². The simultaneous highest τ_eff and lowest density of interface states indicated that the formation of hydrogen bonds at the SiO_x/c-Si interface played an important role in surface passivation of p-type silicon.     

Composite SiOx/fluorocarbon plasma polymer films prepared by r.f. magnetron sputtering of SiO2 and PTFE

Composite films SiO_x/fluorocarbon plasma polymers were prepared by r.f. sputtering from two balanced magnetrons equipped with polytetrafluoroethylene (PTFE) and silica (SiO₂) targets. Argon was used as the working gas. The obtained films were characterised by means of XPS, RBS, FTIR, AFM, TEM, microhardness and static contact angle measurements. The obtained SiO_x/fluorocarbon plasma polymer films reveal different wettability (static contact angle of water ranges from 68° to 40°) and hardness (ranges from 720 to 3200 N/mm²) when the volume fraction ratio (filling factor) of SiO₂ changes from 0.01 to 0.7. The concentration of elements determined by RBS/ERDA varies strongly over this range of filling factors. The heterogeneous structure of the composite films is indicated by TEM at high SiO_x contents.     

On the nitrogen and oxygen incorporation in plasma-enhanced chemical vapor deposition (PECVD) SiOxNy films

Silicon oxynitride films were deposited by plasma-enhanced chemical vapor deposition at low temperatures using nitrous oxide (N₂O) and silane (SiH₄) as gas precursors. The influence of the N₂O/SiH₄ flow ratio (varied from 0.25 up to 5) and the thickness of the films on the optical and structural properties of the material was analyzed. The films were characterized by ellipsometry, Fourier-transform infrared spectroscopy, Rutherford backscattering spectroscopy and optical absorption. Two distinct types of material were obtained, silicon dioxide-like oxynitrides SiO_2−xN_x and silicon-rich oxynitrides SiO_xN_y (x+y<2). The results demonstrate that in silicon dioxide-like material, the nitrogen concentration can be adequately controlled (within the range 0–15 at.%) with total hydrogen incorporation below 5 at.% and no appreciable SiH bonds. It is also shown that the composition remains uniform through the entire thickness of the films. Furthermore, a linear relation between the refractive index and the nitrogen concentration is observed, which makes this material very attractive for optoelectronic applications. On the other hand, silicon-rich material is similar to amorphous silicon, and presents an increasing concentration of SiH bonds, increasing refractive index and decreasing optical gap, which makes it promising for applications in light-emitting devices.     

Optical and dielectric properties of thin SiOx films of variable composition

The effect of the composition of amorphous SiO_x films produced by the vacuum evaporation of SiO, on their optical and dielectric properties was investigated. The variation in the composition of the films was achieved by changing the deposition rate and the pressure of the residual gases.The optical band gap was observed to increase from 2.2 to 3.1 eV as the deposition rate was decreased from 50 to 5 Å s^-1 and simultaneously the refractive index, the permittiviity and the dielectric loss factor were found to decrease. The composition and structure of the films were determined from the optical absorption and IR spectroscopy.The experimental results revealed that SiO_x films produced by vacuum evaporation do not comprise a simple mixture of silicon and SiO₂ phases but they have a single-phase structure.     

Protection of organic light-emitting diodes over 50 000 hours by Cat-CVD SiNx/SiOxNy stacked thin films

Silicon oxynitride (SiO_xN_y) films have been formed by adding proper amount of oxygen gas to usual forming condition of silicon nitride (SiN_x) films in catalytic chemical vapor deposition (Cat-CVD) method. The composition and refractive index of the film can be systematically controlled by changing oxygen flow rate. Organic light-emitting diodes (OLEDs) covered with SiN_x/SiO_xN_y stacked films have been completely protected from damage due to oxygen and moisture and their initial emission intensity is maintained over 1000 hours under 60 °C and 90% RH, which is equivalent to 50 000 hours in normal temperature and humidity conditions.     

Effects of cetyltrimethylammonium bromide on redox deposition and rectification properties of silicon oxide thin film

Silicon oxide (SiO_x) thin film was deposited onto fluorine-doped tin oxide (FTO) and silicon wafer substrate by the reduction of an aqueous solution containing ammonium hexafluorosilicate, dimethylamine borane and cetyltrimethylammonium bromide (CTAB). Characterization of the films by X-ray photoelectron spectroscopic depth profile and infrared spectroscopy proved that the addition of CTAB into the film enhanced the aggregation of silica particles and the growth rate. The SiO_x films (resistivity: 3.2 × 10⁸ Ω cm) remarkably improved the rectification properties of FTO/SiO_x/poly(3,4-ethylenedioxythiophene) derivative diodes. A rectification mechanism based on conduction of electron and ions was investigated.     

Effect of the ion bombardment energy on silicon dioxide films deposited from oxygen/tetraethoxysilane plasmas in a helicon reactor

Silicon dioxide films are deposited on silicon substrates from oxygen/tetraethoxysilane (TEOS) plasmas in a helicon reactor operated at low pressure (5 mtorr). The effect of the negative dc self-bias voltage V_b (0 to −200 V) on structural and electrical bulk properties of SiO₂ films is investigated. The structural characterization has been performed using Fourier-transform infrared (FTIR) spectroscopy, spectroscopic ellipsometry and wet etching. Electrical measurements including capacitance–voltage (C–V), current–voltage (I–V) and constant current stressing (CCS) have been carried out on metal–oxide–semiconductor (MOS) capacitors. As soon as a dc self-bias is applied (∣V_b∣≥50 V), a significant enhancement of the oxide quality is observed in terms of macroscopic densification and reduction in the porosity. These modifications in the structural properties of the deposited SiO₂ films are correlated with an improvement in the I–V characteristics but C–V and CCS measurements revealed that limiting the substrate bias at −50 V leads to best quality silicon dioxide films.     

Dielectric properties of sol-gel derived high-k titanium silicate thin films

High-k dielectric titanium silicate (Ti_xSi_1 − xO₂) thin films have been deposited by means of an optimized sol-gel process. At the optimal firing temperature of 600 °C, the Ti_0.5Si_0.5O₂ films are shown to exhibit not only a dielectric constant (k) as high as ∼ 23 but more importantly the lowest leakage current and dielectric losses. Fourier transform infrared spectroscopy shows an absorbance peak at 930 cm^− 1, which is a clear signature of the formation of Ti-O-Si bondings in all the silicate films. The developed sol-gel process offers the required latitude to grow Ti_xSi_1 − xO₂ with any composition (x) in the whole 0 ≤ x ≤ 1 range. Thus, the k value of the Ti_xSi_1 − xO₂ films can be tuned at any value between that of SiO₂ (3.8) to that of TiO₂ (k ∼ 60) by simply controlling the TiO₂ content of the films. The composition dependence of the dielectric constant of the Ti_xSi_1 − xO₂ films is analyzed in the light of existing models for dielectric composites.     

Effects of annealing atmosphere and substrate on the photoluminescence and Raman scattering from Si nanocrystals in a SiO2 matrix

Thin films of SiO _x have been prepared on quartz or c-Si substrates by thermal evaporation of SiO in vacuum and post-annealed at 1373 K in an argon or hydrogen atmosphere. High-resolution electron microscopy has shown the existence of silicon nanocrystals in the annealed films, and this result has been confirmed by Raman scattering. Photoluminescence has been observed from annealed films and attributed to radiative recombination in Si nanocrystals. Its intensity is appreciably higher upon annealing in Ar than in H₂. It is shown that substrates strongly affect the Raman scattering from Si nanocrystals in nc-Si–SiO₂ thin films with low filling factors.     

Optical and structural properties of SiOx films from ion-assisted deposition

This study investigates the optical and structural properties of SiO_x (x ∼ 1) films prepared by an ion-assisted deposition (IAD) process. The films were prepared by evaporating silicon monoxide, with and without simultaneous Ar⁺ bombardment. The stoichiometry of each film was determined as measured by the infrared spectrometry and X-ray photoelectron spectrometry. The variation in the stoichiometry revealed that the oxygen content of the SiO_x thin films varied slightly under the different conditions of the Ar⁺ bombardment. The results of the X-ray diffraction and transmission electron microscopy (TEM) measurements illustrated that all of the films had amorphous structures. However, a different interfacial appearance between the film and the substrate was observed from the TEM image. The optical constants of the SiO_x thin films were determined by a spectroscopic ellipsometry. The extinction coefficient of all of the films approached zero in the infrared wavelength range from 2 to 7 μm, but the refractive index was varied by the IAD process. The variation of these refractive indices is mainly related to the packing density of the films.