MOS devices with tetragonal ZrO2 as gate dielectric formed by annealing ZrO2/Ge/ZrO2 laminate

A Ge-stabilized tetragonal ZrO₂ (t-ZrO₂) film with permittivity (κ) of 36.2 was formed by depositing a ZrO₂/Ge/ZrO₂ laminate and a subsequent annealing at 600 °C, which is a more reliable approach to control the incorporated amount of Ge in ZrO₂. On Si substrates, with thin SiON as an interfacial layer, the SiON/t-ZrO₂ gate stack with equivalent oxide thickness (EOT) of 1.75 nm shows tiny amount of hysteresis and negligible frequency dispersion in capacitance-voltage (C-V) characteristics. By passivating leaky channels derived from grain boundaries with NH₃ plasma, good leakage current of 4.8 × 10⁻⁸ A/cm² at V_g = V_fb − 1 V is achieved and desirable reliability confirmed by positive bias temperature instability (PBTI) test is also obtained.     

Effective formation of interface controlled Y2O3 thin film on Si(1 0 0) in a metal-(ferroelectric)-insulator-semiconductor structure

Yttrium was deposited on the chemical oxide of Si and annealed under vacuum to control the interface for the formation of Y₂O₃ as an insulating barrier to construct a metal-ferroelectric-insulator-semiconductor structure. Two different pre-annealing temperatures of 600 and 700 °C were chosen to investigate the effect of the interface state formed after the pre-annealing step on the successive formation of Y₂O₃ insulator and Nd₂Ti₂O₇ (NTO) ferroelectric layer through annealing under an oxygen atmosphere at 800 °C. Pre-anneal treatments of Y-metal/chemical-SiO₂/Si at 600 and 700 °C induced a formation of Y₂O₃ and Y-silicate, respectively. The difference in the pre-anneal temperature induced almost no change in the electrical properties of the Y₂O₃/interface/Si system, but degraded properties were observed in the NTO/Y₂O₃/interface/Si system pre-annealed at 600 °C when compared with the sample pre-annealed at 700 °C. C-V characteristics of the NTO/Y₂O₃/Si structured system showed a clockwise direction of hysteresis, and this gap could be used as a memory window for a ferroelectric-gate. A smaller hysteric gap and electrical breakdown values were observed in the NTO/Y₂O₃/Si system pre-annealed at 600 °C, and this was due to an unintentional distribution of the applied field from the presence of an interfacial layer containing Y-silicate and SiO₂ phases.     

Electrical properties of vacuum annealed La2O3 thin films grown by E-beam evaporation

In this article, the conduction mechanisms of metal-oxide-semiconductor with vacuum annealed Lanthana (La₂O₃) oxide film are investigated. Lanthana films with thicknesses of 3.5, 4.7, and 11 nm were deposited by E-beam evaporation on n-Si (100), and annealed at various temperatures (300-500 °C) in ultra-high vacuum (10⁻¹⁰-10⁻⁹ Torr) for 90 min. From the measurement of spectroscopic ellipsometry, it is found that film thickness is increased with annealing temperature, which would be cause of flat-band voltage shift (ΔV_FB) due to the growth of interfacial layer. From the capacitance measurement, it is found that ΔV_FB of the film is reduced by post-deposition anneal (PDA) compared to that of as-deposited film, but increase again at high temperature annealing, especially in the case of thin film (3.5 nm). From the applied voltage and temperature dependence of the leakage current of the film, with different gate electrode materials (Ag, Al, and Pt), it is shown that the leakage currents are associated with ohmic and Poole-Frenkel (P-F) conductions when flat-band voltage (V_FB) is less than zero, and ohmic and Space-Charge-Limited Current (SCLC) conductions when V_FB is greater than zero. The dielectric constants obtained from P-F conduction for Al gate electrode case is found to be 11.6, which is consistent with the C-V result 11.9. Barrier height of trap potential well is found to be 0.24 eV from P-F conduction. Based on SCLC theory, leakage currents of 3.5 and 11 nm films with different PDA temperatures are explained in terms of oxide trap density.     

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.     

Comparative study of AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors with Al2O3 and HfO2 gate oxide

AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors (MOSHFETs) with Al₂O₃ gate oxide which was deposited by atomic layer deposition (ALD) were fabricated and their performance was then compared with that of AlGaN/GaN MOSHFETs with HfO₂ gate oxide. The capacitance (C)-voltage (V) curve of the Al₂O₃/GaN MOS diodes showed a lower hysteresis and lower interface state density than the C-V curve of the HfO₂/GaN diodes, indicating better quality of the Al₂O₃/GaN interface. The saturation of drain current in the I_D-V_GS relation of the Al₂O₃ AlGaN/GaN MOSHFETs was not as pronounced as that of the HfO₂ AlGaN/GaN MOSHFETs. The gate leakage current of the Al₂O₃ MOSHFET was five to eight orders of magnitude smaller than that of the HfO₂ MOSHFETs.     

Effects of annealing schedule on orientations of Bi3.2Nd0.8Ti3O12 ferroelectric films prepared by metalorganic solution deposition

Fatigue-free Bi_3.2Nd_0.8Ti₃O₁₂ ferroelectric thin films were successfully prepared on p-Si(1 1 1) substrate using metalorganic solution deposition process. The orientation and formation of thin film under different annealing schedules were studied using XRD and AFM. XRD analysis indicated that (2 0 0)-oriented films with degree of orientation of I₍₂₀₀₎/I₍₁₁₇₎ = 2.097 and 0.466 were obtained by preannealing the film at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min, 10 min and 20 min, respectively, (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 1.706 were obtained by rapid thermal annealing the film at 700 °C for 3 min without preannealing, and (0 0 8)-oriented film with degree of orientation of I₍₀₀₈₎/I₍₁₁₇₎ = 0.719 were obtained by preheating the film from room temperature to 700 °C at 20 °C/min followed by annealing for 10 min. The a-axis and c-axis orientation decreased as increase in annealing time due to effects of (1 1 1)-oriented substrate. AFM analysis further indicated that preannealing at 400 °C for 10 min followed by rapid thermal annealing at 700 °C for 3 min resulted in formation of platelike crystallite parallel to substrate surface, however rapid thermal annealing at 700 °C for 3 min without preannealing resulted in columnar crystallite perpendicular to substrate surface.     

Composition and electrical characteristics of Al2O3-HfO2-HfTiO nanolaminates on Si

A dielectric constant of 27 was demonstrated in the as deposited state of a 5 nm thick, seven layer nanolaminate stack comprising Al₂O₃, HfO₂ and HfTiO. It reduces to an effective dielectric constant (k_eff) of ∼14 due to a ∼0.8 nm interfacial layer. This results in a quantum mechanical effective oxide thickness (EOT) of ∼1.15 nm. After annealing at 950 °C in an oxygen atmosphere k_eff reduces to ∼10 and EOT increases to 1.91 nm. A small leakage current density of about 8 × 10⁻⁷ and 1 × 10⁻⁴ A/cm², respectively at electric field 2 and 5 MV/cm and a breakdown electric field of about 11.5 MV/cm was achieved after annealing at 950 °C.     

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.     

Investigation of Ta2O5/SiO2/4H-SiC MIS capacitors

Tantalum pentoxide (Ta₂O₅) deposited by pulsed DC magnetron sputtering technique as the gate dielectric for 4H-SiC based metal-insulator-semiconductor (MIS) structure has been investigated. A rectifying current-voltage characteristic was observed, with the injection of current occurred when a positive DC bias was applied to the gate electrode with respect to the n type 4H-SiC substrate. This undesirable behavior is attributed to the relatively small band gap of Ta₂O₅ of around 4.3 eV, resulting in a small band offset between the 4H-SiC and Ta₂O₅. To overcome this problem, a thin thermal silicon oxide layer was introduced between Ta₂O₅ and 4H-SiC. This has substantially reduced the leakage current through the MIS structure. Further improvement was obtained by annealing the Ta₂O₅ at 900 °C in oxygen. The annealing has also reduced the effective charge in the dielectric film, as deduced from high frequency C-V measurements of the Ta₂O₅/SiO₂/4H-SiC capacitors.     

Properties of ALD HfTaxOy high-k layers deposited on chemical silicon oxide

HfTa_xO_y high-k dielectric layers with different compositions were deposited using ALD on 1 nm SiO₂ generated by ozone based cleaning of 200 mm Si(1 0 0) surface. Physical characterization of blanket layers and C-V mapping demonstrates that the ALD layers have excellent uniformity and controllable compositions. The layers with a composition of HfTaO_5.5 remain amorphous after annealing at 900 °C. The C-V measurements of MOS capacitors show no hysteresis, negligible frequency dispersion and interfacial state density smaller than 3 × 10¹¹ (cm⁻² eV⁻¹). k-value of the amorphous layers varies in the range from 20 to 25, depending on layer composition. The flat band voltage does not shift with the increase of EOT, implying that the effect of fixed charge densities in the layers is negligible. The I-V measurements show a leakage reduction comparable to that of the ALD HfO₂ layers.     

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.     

Infrared spectroscopy and X-ray diffraction studies on the crystallographic evolution of La2O3 films upon annealing

Rare earth oxides (REOs) have lately received extensive attention in relation to the continuous scaling down of non-volatile memories (NVMs). In particular, La₂O₃ films are promising for integration into future NVMs because they are expected to crystallize above 400 °C in the hexagonal phase (h-La₂O₃) which has a higher κ value than the cubic phase (c-La₂O₃) in which most of REOs crystallize. In this work, La₂O₃ films are grown on Si by atomic layer deposition using La(C₅H₅)₃ and H₂O. Within the framework of the h-La₂O₃ formation, we systematically study the crystallographic evolution of La₂O₃ films versus annealing temperature (200-600 °C) by Fourier transform infrared spectroscopy (FTIR) and grazing incidence X-ray diffraction (GIXRD). As-grown films are chemically unstable in air since a rapid transformation into monoclinic LaO(OH) and hexagonal La(OH)₃ occurs. Vacuum annealing of sufficiently thick (>100 nm) La(OH)₃ layers induces clear changes in FTIR and GIXRD spectra: c-La₂O₃ gradually forms in the 300-500 °C range while annealing at 600 °C generates h-La₂O₃ which exhibits, as inferred from our electrical data, a desirable κ ∼ 27. A quick transformation from h-La₂O₃ into La(OH)₃ occurs due to H₂O absorption, indicating that the annealed films are chemically unstable. This study extends our recent work on the h-La₂O₃ formation.     

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.     

A novel thermally-stable zirconium amidinate ALD precursor for ZrO2 thin films

ZrO₂ thin films were deposited by the atomic layer deposition process on Si substrates using tetrakis(N,N′-dimethylacetamidinate) zirconium (Zr-AMD) as a Zr precursor and H₂O as an oxidizing agent. Tetrakis (ethylmethylamino) zirconium (TEMA-Zr) was also evaluated for a comparative study. Physical properties of ALD-derived ZrO₂ thin films were studied using ellipsometry, grazing incidence XRD (GI-XRD), high resolution TEM (HRTEM), and atomic force microscopy (AFM). The ZrO₂ deposited using Zr-AMD showed a better thermal stability at high substrate temperature (>300 °C) compared to that using TEMA-Zr. GI-XRD analysis reveals that after 700 °C anneal both ZrO₂ films enter tetragonal phase. The electrical properties of N₂-annealed ZrO₂ film using Zr-AMD exhibit an EOT of 1.2 nm with leakage current density as low as 2 × 10⁻³ A/cm² (@V_fb−1 V). The new Zr amidinate is a promising ALD precursor for high-k dielectric applications.     

Materials and interfaces issues in pentacene/PTCDI-C8 ambipolar organic field-effect transistors with solution-based gelatin dielectric

Gelatin is a natural protein, which works well as the gate dielectric for pentacene/N,N-dioctyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C₈) ambipolar organic field-effect transistors (OFETs) in air ambient and in vacuum. An aqueous solution process was used to form the gelatin gate dielectric film on poly(ethylene terephthalate) (PET) by spin-coating and subsequent casting. Pentacene morphology and interface roughness are two major factors affecting the electron and hole field-effect mobility (μ_FE) values of pentacene/PTCDI-C₈ ambipolar OFETs in vacuum and in air ambient. In contrast, water absorption in gelatin has higher contribution to the electron and hole μ_FE values in air ambient. The ambipolar performance of pentacene/PTCDI-C₈ ambipolar OFETs depends on their layer sequence. For example, when PTCDI-C₈ is deposited onto pentacene, i.e. in the structure of PTCDI-C₈/pentacene, unbalanced ambipolar characteristics appear. In contrast, better ambipolar performance occurs in the structure of pentacene/PTCDI-C₈. The optimum ambipolar characteristics with electron μ_FE of 0.85 cm² V⁻¹ s⁻¹ and hole μ_FE of 0.95 cm² V⁻¹ s⁻¹ occurs at the condition of pentacene (40 nm)/PTCDI-C₈ (40 nm). Surprisingly, water absorption plays a crucial role in ambipolar performance. The device performance changes tremendously in pentacene/PTCDI-C₈ ambipolar OFETs due to the removal of water out of gelatin in vacuum. The optimum ambipolar characteristics with electron μ_FE of 0.008 cm² V⁻¹ s⁻¹ and hole μ_FE of 0.007 cm² V⁻¹ s⁻¹ occurs at the condition of pentacene (65 nm)/PTCDI-C₈ (40 nm). The roles of layer sequence, relative layer thickness, and water absorption are proposed to explain the ambipolar performance.     

A flip-chip packaged 80-nm In0.7Ga0.3As MHEMT for millimeter-wave low-noise applications

In this paper, we present a flip-chip 80-nm In_0.7Ga_0.3As MHEMT device on an alumina (Al₂O₃) substrate with very little decay on device RF performance up to 60 GHz. After package, the device exhibited high I_DS = 435 mA/mm at V_DS = 1.5 V, high g_m = 930 mS/mm at V_DS = 1.3 V, the measured gain was 7.5 dB and the minimum noise figure (NF_min) was 2.5 dB at 60 GHz. As compared to the bare chip, the packaged device exhibited very small degradation in performance. The result shows that with proper design of the matching circuits and packaging materials, the flip-chip technology can be used for discrete low noise FET package up to millimeter-wave range.     

A low gate leakage current and small equivalent oxide thickness MOSFET with Ti/HfO2 high-k gate dielectric

Annealing effects on electrical characteristics and reliability of MOS device with HfO₂ or Ti/HfO₂ high-k dielectric are studied in this work. For the sample with Ti/HfO₂ higher-k dielectric after a post-metallization annealing (PMA) at 600 °C, its equivalent oxide thickness value is 7.6 Å and the leakage density is about 4.5 × 10⁻² A/cm². As the PMA is above 700 °C, the electrical characteristics of MOS device would be severely degraded.     

Co gamma irradiation effects on electrical characteristics of Al/Y2O3/n-Si/Al capacitors

Al/Y₂O₃/n-Si/Al capacitors were irradiated by using a ⁶⁰Co gamma ray source and a maximum dose up to 8.4 kGy. The effect of an annealing treatment performed at 600 or 900 °C on the yttrium oxide (Y₂O₃) films was investigated by XRD and Raman spectroscopy. High-frequency capacitance-voltage (C-V) and conductance-voltage (G-V) measurements as well as quasi-static measurements of the MOS structures were analysed. The annealing improves the crystalline state of the Y₂O₃ thin film material and decreases the values of the flat-band voltage and of the interface trap level density indicating an improvement of the electrical properties of the interface thin film-substrate. But at this interface, the formation of an yttrium-silicate layer was also evidenced. After gamma irradiation, the values of the flat-band voltage and of the interface trap level density related to the Al/Y₂O₃/n-Si/Al structure increase and especially for the structure made with the materials annealed at 900 °C for 1 h. In that case, the structure is very sensitive to a gamma irradiation dose up to 8.4 kGy.     

Effects of high doping on the bandgap bowing for AlxGa1−xN

This paper gives the composition dependence of the bandgap energy for highly doped n-type Al_xGa_1−xN. We report results of the bowing parameter obtained using a random simulation. Three groups of Al_xGa_1−xN semiconductors were considered and which are distinguishable by their non degenerate or degenerate character in the doping density (10¹⁷?N_D?10²⁰ cm⁻³). A striking feature is the large discrepancy of the bandgap bowing (−2.02?b?2.94 eV), as was demonstrated from our calculations. This suggests that high doping may be a possible cause able to induce the large range of bowing parameters reported for Al_xGa_1−xN alloys.     

Annealing effect on the metal gate effective work function modulation for the Al/TiN/SiO2/p-Si structure

In this work, the thermal annealing effect on the metal gate effective work function (EWF) modulation for the Al/TiN/SiO₂/p-Si(1 0 0) structure was investigated. Compared with the sample of TiN/SiO₂/p-Si(1 0 0) structure, for the sample additionally capped with Al the flat band voltage has a very obvious shift as large as 0.54 V to the negative direction after forming gas annealing. It is also revealed that the thermal budget can effectively influence both the EWF of the gate electrode and the thickness of the gate dielectric layer when a post annealing at 600 °C with different soak times was applied to the samples with Al cap. Material characterization indicates that the diffusion of Al and the formation of Al oxide during annealing should be responsible for all the phenomena. The interface trap density Dit calculated from the high-frequency C-V and the laser-assisted high-frequency C-V curves show that the introduction of Al does not cause reliability problem in the Al/TiN/SiO₂/p-Si structure.