Neste trabalho foi realizada a investigação de interações hiperfinas em amostra nano estruturadas e filmes finos de dióxido de háfnio por meio da técnica de correlação angular gama-gama perturbada (CAP), com o intuito de realizar um estudo sistemático do comportamento dos parâmetros quadrupolares com a temperatura de tratamento térmico. Para a realização destas medidas foi utilizada a ponta de prova 181Hf -> 181Ta que foi produzida na própria amostra por irradiação, no reator IEA-R1 do IPEN. As amostras foram obtidas através do processo químico sol-gel e as análises dos compostos realizadas por difração de raios-X, EDS e MEV. As amostras em forma de pó foram todas produzidas pelo Laboratório de Interações Hiperfinas do IPEN, no entanto o filme fino com espessura de 10nm foi produzido pelo Centro de Lasers e Aplicações (CLA) do IPEN e o filme fino de espessura de 409nm foi produzido pelo Laboratório de Interações Hiperfinas da Universidade de Lisboa. As medidas foram realizadas todas à temperatura ambiente e os resultados mostraram que a fase monoclínica encontra-se presente em todas as amostras e sua fração tende a aumentar sempre com o aumento da temperatura de tratamento térmico na qual foram submetidas às amostras. A impurificação de algumas amostras com elementos Co e Fe foi realizada com a intenção de se observar o comportamento da amostra em função da temperatura de tratamento térmico e também verificar a existência de ferromagnetismo à temperatura ambiente. / Hyperfine interactions in the powder samples and nanostructured thin films of hafnium dioxide have been studied through the perturbed angular correlation (PAC) technique in order to perform a systematic study of the behavior of quadrupole parameters with the annealing temperature. The PAC measurements were performed with the 181Hf -> 181Ta probe. The probe was produced by the neutron irradiation in the IEA-R1 nuclear reactor of IPEN. Samples were prepared using sol-gel chemical process. The samples were analyzed by X-ray diffraction, SEM and EDS. The powder samples were all produced in the Laboratory of Hyperfine Interactions of IPEN, however the thin film with a thickness of 10nm was produced by the Lasers and Applications Center (CLA) of IPEN and the thin film of a thickness of 409nm were produced by the Hyperfine Interactions Laboratory of the Lisbon University. All the measurements were perform at room temperature and showed that the monoclinic phase is present in all the samples and their fraction tends to increase with increasing annealing temperature to which the samples were submitted. Some of the samples were doped with 3d elements Co and Fe in order to observe the possible existence of ferromagnetism at room temperature.

Neste trabalho, foram caracterizados eletricamente capacitores MOS com alumina (Al2O3) e aluminato de háfnio (AlxHf1-xOy) como dielétricos de porta, além disso, estes filmes dielétricos foram caracterizados fisicamente. A alumina foi obtida da oxidação anódica de filmes de alumínio evaporados sobre p-Si (100) através de imersão em ácido nítrico por 4 ou 6 min, para diferentes etapas de limpeza finais do substrato: solução diluída de ácido fluorídrico (DHF) ou solução de peróxido sulfúrico (SPM). Análises de retroespalhamento de Rutherford (RBS), espectroscopia por dispersão em energia (EDS) e espectroscopia por dispersão de comprimento de onda (WDS) indicam a formação da alumina estequiométrica, sendo que a difração de raios-X (XRD), mostrou o caráter amorfo do dielétrico. Por intermédio de curvas capacitância x tensão (CV) foram obtidas a espessura equivalente ao óxido de silício (EOT2,8nm), a densidade de estados de interface (Dit1,4x1011ev-1cm-2) e a permissividade elétrica da alumina (high-k10,6). A admitância associada à corrente de fuga em capacitores MOS foi modelada através de emissão por Frenkel-Poole, tunelamento por Fowler-Nordheim e/ou corrente de fuga constante. Os aluminatos de háfnio (AlxHf1-xOy) foram obtidos sobre p-Si (100), através de deposição atômica por camadas (ALD) para diferentes proporções molares de háfnio (25, 50 ou 75%) e para diferentes tratamentos posteriores (1000ºC, 60s em N2 ou N2+O2 ou laser). A espessura e a rugosidade foram obtidas com a ajuda da técnica de reflectometria de raios-X (XRR). A proporção molar de háfnio adotada no processo de obtenção dos filmes foi confirmada através de análises RBS e WDS. Por XRD, foi verificado o caráter amorfo e a separação de fases nos aluminatos e, por espalhamento de raios-X em ângulo-rasante e pequena abertura (GISAXS), foram analisadas as novas fases formadas. Por fim, da análise CV, foram obtidos EOT9,54nm, resistência série (Rs68,3) e a permissividade elétrica para o aluminato de háfnio (high-k15,2). Finalmente, uma modelagem da admitância associada à corrente de fuga em função da frequência foi proposta para as estruturas MOS. / In this work, MOS capacitors were electrically characterized using alumina (Al2O3) and hafnium aluminate (AlxHf1-xOy) as gate dielectrics; also, the same dielectrics films were physically characterized. Anodic alumina was obtained from oxidation of evaporated aluminum films immersed in nitric acid for 4 or 6 min for different last step cleanings of the p-Si (100) substrates: diluted hydrofluoric acid (DHF) or sulfur peroxide mixture (SPM). Rutherford Backscattering (RBS), Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS) have shown the formation of stoichiometric alumina and the dielectric amorphous structure was revealed by X-Ray Diffraction (XRD). From Capacitance x Voltage curves (CV), it was obtained the equivalent oxide thickness (EOT2.8nm), interface trap density (Dit1.4x1011ev-1cm-2) and Al2O3 dielectric constant (high-k10.6). The admittance that represents the leakage process was modeled according to Frenkel-Poole emission, Fowler-Nordheim tunneling and/or constant leakage admittance. Hafnium aluminates (AlxHf1-xOy) were obtained on (100) silicon wafer surfaces by Atomic Layer Deposition (ALD) for different hafnium molar ratios (25, 50 or 75%) and for different treatments (1000ºC, 60s in N2 or N2+O2 or laser). Thickness and roughness were extracted from X-Ray Reflectometry (XRR) spectra. The hafnium molar ratios used in ALD process were confirmed by RBS and WDS. XRD analysis was used to establish the amorphous structure and phase separation in the aluminates after thermal treatments and Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) was used to analyze the new phases formed. From CV analysis, it was extracted EOT9.54nm, series resistance (Rs68.3) and dielectric constant from hafnium aluminate (high-k15.2). Finally, the admittance that represents the leakage was modeled in function of the frequency for the MOS structures.

Neste trabalho foi realizada a investigação de interações hiperfinas em amostra nano estruturadas e filmes finos de dióxido de háfnio por meio da técnica de correlação angular gama-gama perturbada (CAP), com o intuito de realizar um estudo sistemático do comportamento dos parâmetros quadrupolares com a temperatura de tratamento térmico. Para a realização destas medidas foi utilizada a ponta de prova 181Hf -> 181Ta que foi produzida na própria amostra por irradiação, no reator IEA-R1 do IPEN. As amostras foram obtidas através do processo químico sol-gel e as análises dos compostos realizadas por difração de raios-X, EDS e MEV. As amostras em forma de pó foram todas produzidas pelo Laboratório de Interações Hiperfinas do IPEN, no entanto o filme fino com espessura de 10nm foi produzido pelo Centro de Lasers e Aplicações (CLA) do IPEN e o filme fino de espessura de 409nm foi produzido pelo Laboratório de Interações Hiperfinas da Universidade de Lisboa. As medidas foram realizadas todas à temperatura ambiente e os resultados mostraram que a fase monoclínica encontra-se presente em todas as amostras e sua fração tende a aumentar sempre com o aumento da temperatura de tratamento térmico na qual foram submetidas às amostras. A impurificação de algumas amostras com elementos Co e Fe foi realizada com a intenção de se observar o comportamento da amostra em função da temperatura de tratamento térmico e também verificar a existência de ferromagnetismo à temperatura ambiente. / Hyperfine interactions in the powder samples and nanostructured thin films of hafnium dioxide have been studied through the perturbed angular correlation (PAC) technique in order to perform a systematic study of the behavior of quadrupole parameters with the annealing temperature. The PAC measurements were performed with the 181Hf -> 181Ta probe. The probe was produced by the neutron irradiation in the IEA-R1 nuclear reactor of IPEN. Samples were prepared using sol-gel chemical process. The samples were analyzed by X-ray diffraction, SEM and EDS. The powder samples were all produced in the Laboratory of Hyperfine Interactions of IPEN, however the thin film with a thickness of 10nm was produced by the Lasers and Applications Center (CLA) of IPEN and the thin film of a thickness of 409nm were produced by the Hyperfine Interactions Laboratory of the Lisbon University. All the measurements were perform at room temperature and showed that the monoclinic phase is present in all the samples and their fraction tends to increase with increasing annealing temperature to which the samples were submitted. Some of the samples were doped with 3d elements Co and Fe in order to observe the possible existence of ferromagnetism at room temperature.

Neste trabalho, foram caracterizados eletricamente capacitores MOS com alumina (Al2O3) e aluminato de háfnio (AlxHf1-xOy) como dielétricos de porta, além disso, estes filmes dielétricos foram caracterizados fisicamente. A alumina foi obtida da oxidação anódica de filmes de alumínio evaporados sobre p-Si (100) através de imersão em ácido nítrico por 4 ou 6 min, para diferentes etapas de limpeza finais do substrato: solução diluída de ácido fluorídrico (DHF) ou solução de peróxido sulfúrico (SPM). Análises de retroespalhamento de Rutherford (RBS), espectroscopia por dispersão em energia (EDS) e espectroscopia por dispersão de comprimento de onda (WDS) indicam a formação da alumina estequiométrica, sendo que a difração de raios-X (XRD), mostrou o caráter amorfo do dielétrico. Por intermédio de curvas capacitância x tensão (CV) foram obtidas a espessura equivalente ao óxido de silício (EOT2,8nm), a densidade de estados de interface (Dit1,4x1011ev-1cm-2) e a permissividade elétrica da alumina (high-k10,6). A admitância associada à corrente de fuga em capacitores MOS foi modelada através de emissão por Frenkel-Poole, tunelamento por Fowler-Nordheim e/ou corrente de fuga constante. Os aluminatos de háfnio (AlxHf1-xOy) foram obtidos sobre p-Si (100), através de deposição atômica por camadas (ALD) para diferentes proporções molares de háfnio (25, 50 ou 75%) e para diferentes tratamentos posteriores (1000ºC, 60s em N2 ou N2+O2 ou laser). A espessura e a rugosidade foram obtidas com a ajuda da técnica de reflectometria de raios-X (XRR). A proporção molar de háfnio adotada no processo de obtenção dos filmes foi confirmada através de análises RBS e WDS. Por XRD, foi verificado o caráter amorfo e a separação de fases nos aluminatos e, por espalhamento de raios-X em ângulo-rasante e pequena abertura (GISAXS), foram analisadas as novas fases formadas. Por fim, da análise CV, foram obtidos EOT9,54nm, resistência série (Rs68,3) e a permissividade elétrica para o aluminato de háfnio (high-k15,2). Finalmente, uma modelagem da admitância associada à corrente de fuga em função da frequência foi proposta para as estruturas MOS. / In this work, MOS capacitors were electrically characterized using alumina (Al2O3) and hafnium aluminate (AlxHf1-xOy) as gate dielectrics; also, the same dielectrics films were physically characterized. Anodic alumina was obtained from oxidation of evaporated aluminum films immersed in nitric acid for 4 or 6 min for different last step cleanings of the p-Si (100) substrates: diluted hydrofluoric acid (DHF) or sulfur peroxide mixture (SPM). Rutherford Backscattering (RBS), Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS) have shown the formation of stoichiometric alumina and the dielectric amorphous structure was revealed by X-Ray Diffraction (XRD). From Capacitance x Voltage curves (CV), it was obtained the equivalent oxide thickness (EOT2.8nm), interface trap density (Dit1.4x1011ev-1cm-2) and Al2O3 dielectric constant (high-k10.6). The admittance that represents the leakage process was modeled according to Frenkel-Poole emission, Fowler-Nordheim tunneling and/or constant leakage admittance. Hafnium aluminates (AlxHf1-xOy) were obtained on (100) silicon wafer surfaces by Atomic Layer Deposition (ALD) for different hafnium molar ratios (25, 50 or 75%) and for different treatments (1000ºC, 60s in N2 or N2+O2 or laser). Thickness and roughness were extracted from X-Ray Reflectometry (XRR) spectra. The hafnium molar ratios used in ALD process were confirmed by RBS and WDS. XRD analysis was used to establish the amorphous structure and phase separation in the aluminates after thermal treatments and Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) was used to analyze the new phases formed. From CV analysis, it was extracted EOT9.54nm, series resistance (Rs68.3) and dielectric constant from hafnium aluminate (high-k15.2). Finally, the admittance that represents the leakage was modeled in function of the frequency for the MOS structures.

De nouveaux précurseurs pour LI-MOCVD (Liquid injection Metal Organic Chemical Vapor Deposition) de Hf et de Zr ont été synthétisés et caractérisés par IR-TF, RMN multinoyaux, diffraction des RX sur monocristal et par ATG. La comparaison des comportements thermiques de différents complexes synthétisés a permis d'étudier l'effet de différents groupements sur leur volatilité et leur stabilité thermique. Les mono-amidinates et les monoguanidinates sont apparus plus volatiles et moins stables thermiquement que les di-amidinates et les di-guanidinates. Les films d'oxyde d'hafnium déposés ont été caractérisés par DRX, XRR, ATR et XPS. Les mono-guanidinates asymétriques tel que Hf(NEt2)3(iPr-Et2-tBu-GUA) et les di-guanidinates asymétriques tel que Hf(NMe2)2(Et-Me2-tBu-GUA)2 sont très prometteurs pour le dépôt de couches d'HfO2. Ils permettent la stabilisation d'une phase d'HfO2 de structure cristalline de symétrie supérieur à la phase monoclinique à 580°C. De plus, ces précurseurs permettent l'obtention des films de HfO2 nitruré en absence d'une étape supplémentaire de nitruration

<p>Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO₂, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta₂O₅, zirconium oxide, ZrO₂ and hafnium oxide, HfO₂.</p><p>This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta₂O₅, ZrO₂ and HfO₂ using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition.</p><p>All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al₂O₃(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO₂ deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.</p>

Due to the constantly decreasing dimensions of electronic devices, the conventional dielectric material in transistors and capacitors, SiO2, has to be replaced by a material with higher dielectric constant. Some of the most promising candidates are tantalum oxide,Ta2O5, zirconium oxide, ZrO2 and hafnium oxide, HfO2. This thesis describes new chemical vapour deposition (CVD) and atomic layer deposition (ALD) processes for deposition of Ta2O5, ZrO2 and HfO2 using the metal iodides as starting materials. The layer-by-layer growth in ALD was also studied in real time with a quartz crystal microbalance (QCM) to examine the process characteristics and to find suitable parameters for film deposition. All the processes presented here produced high-purity films at low deposition temperatures. It was also found that films deposited on Pt substrates generally crystallise at lower temperature, or with lower thickness, than on silicon and single-crystalline oxide substrates. Films grown on MgO(001) and α-Al2O3(001) substrates were strongly textured or epitaxial. For example, monoclinic HfO2 deposited on MgO(001) were epitaxial for deposition temperatures of 400-500 C in ALD and 500-600 C in CVD. Electrical characterisation showed that the crystallinity of the films had a strong effect on the dielectric constant, except in cases of very thin films, where the dielectric constant was more dependent on layer thickness.

The continuous scaling of microelectronic devices requires high permittivity (high-k) dielectrics to replace SiO₂ as the gate material. HfO₂ is one of the most promising candidates but the crystallization temperature of amorphous HfO₂ is too low to withstand the fabrication process. To enhance the film thermal stability, HfO₂ is deposited using atomic layer deposition (ALD), and incorporated with various amorphizers, such as La₂O₃, Al₂O₃, and Ta₂O₅. The incorporation is achieved by growing multiple ALD layers of HfO₂ and one ALD layer of MO[subscript x] (M = La, Al, and Ta) alternately (denoted as [xHf + 1M]), and the incorporation concentration can be effectively controlled by the HfO₂-to-MO[subscript x] ALD cycle ratio (the x value). The crystallization temperature of 10 nm HfO₂ increases from 500 °C to 900 °C for 10 nm [xHf + 1M] film, where x = 3, 3, and 1 for M = La, Al, and Ta, respectively. The incorporation of La₂O₃, and Ta₂O₅ will not compromise the dielectric constant of the film because of the high-k nature of La₂O₃, and Ta₂O₅. Angle resolved X-ray photoelectron spectroscopy (AR-XPS) reveals that when the HfO₂-to-MO[scubscript x] ALD cycle ratio is large enough (x > 3 and 4 for La and Al, respectively), periodic structures exist in films grown by this method, which are comprised of repeated M-free HfO₂ ultrathin layers sandwiched between HfM[subscript x]O[scubscript y] layers. Generally, the film thermal stability increases with thinner overall thickness, higher incorporation concentration, and stronger amorphizing capability of the incorporated elements. When the x value is low, the films are more like homogeneous films, with thermal stabilities determined by the film thickness and the amorphizer. When the x value is large enough, the periodically-repeated structure may add an extra factor to stabilize the amorphous phase. For the same incorporation concentration, films with an appropriately high periodicity may have an increased thermal stability. The manner by which the periodic structure and incorporated element affect thermal stability is explored and resolved using nanolaminates comprised of alternating layers of [scubscript y]HfO₂ and [xHf + 1M] × n, where y varied from 2 to 20, x varied from 1 to 2, and n varied from 4 to 22. / text

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