内田 寛

Relationships among in-plane residual stress and some dielectric properties (remanent polarization, coercive field, dielectric permittivity, etc.) were investigated on ferroelectric thin films. Epitaxial PbTiO_3 thin films were deposited on Pt/(100)SrTiO_3 substrate by MOCVD. Residual stresses of the films were determined by a modified sin^2ψ method. The external stress in this study could be varied from +2.0 GPa up to +6.0 GPa. We first observed the change of the dielectric properties together with the tensile stress application in actual experiments; decrease of the remanent polarization from 11 μC・cm^&lt-2> down to 3 μC・cm^<-2> and of the coercive field form 115 kV・cm^<-1> down to 95 kV・cm^<-1>. The Curie temperature of the film was decreased from 450℃ to 437℃ with increasing the residual stress, while the dielectric permittivity at room temperature was measured to be approximately 210, irrespectively of the residual stress. Further, the tensile stress caused deformation of PbTiO_3 crystal lattice, which was described as the decrease of the c/a ratio. We conclude that the residual stress varied the dielectric properties by deforming the crystal lattice.

An analytical technique to determine residual stress in eqitaxial thin film by asymmetric X-ray diffraction (XRD) was studied. The residual stresses of PbTiO_3 films were determied by XRD technique and displace measurement technique. Measurement results by these techniques were compared with each other to consider the respective advantages of each technique. The stresses measured by XRD technique were not consistent with those by displacement measurement technique, because the latter technique involves errors which origined from the shape and the size of the substrate. The stress in a polycrystalline film measured by modified sin^2ψ method was in good agreement with that measured by normal sin^2ψ method. This result suggests that modified sin^2ψ method can be applied to stress measurement not only in epitaxial thin films, but also in polycrystalline thin films. We further discuss the precision of the stress determination technique. Residual stress of epitaxial PbTiO_3 film on (100) SrTiO_3 substrate measured by modified sin^2ψ method was comparable to the theoretical stress estimated from the difference in thermal expansion coefficients between the film and the substrate. Stress values measured by modified sin^2ψ method may thus have the precision required for actual application.

窒化ケイ素マグネシウム (MgSiN₂) の焼結に及ぼす酸化イットリウム (Y₂O₃) 添加の影響を検討した.本論文で検討した焼結条件は, 焼成温度 (1400℃および1500℃), 焼成時間 (1～7h), およびY₂O₃添加量 (1～7mass%) であった.MgSiN₂単味成形体を1500℃で1h焼成したところ, MgSiN₂は部分的に熱分解しα一窒化ケイ素 (Si₃N₄) とβ一Si₃N₄が生成した.一方, 焼結助剤としてY₂O₃を3mass%MgSiN₂に添加したところ, 1500℃で3h焼成してもMgSiN₂の熱分解が起こらなかった.Y₂O₃の添加量を3～7mass%まで増加させると, Y2Si₃O₃N₄の生成と生成量の増加が認められた.MgSiN₂成形体を1500℃で3h焼成したところ, Y₂O₃無添加の場合の相対密度は約67%であったが, 3mass%Y₂O₃添加の場合には約90%となった.Y₂O₃の添加量を3～7mass%まで増加させると, MgSiN₂焼結体の曲げ強度は160MPaから200MPaまで増加したが, 熱伝導率は15～18W・m-1・K-1の範囲であった.

Magnesium silicon nitride (MgSiN2) powder was prepared by carbothermally reducing a magnesium metasilicate whose chemical composition corresponded to MgO . SiO2 or MgSiO3. About 0.2 g of the powder mixture of magnesium metasilicate and carbon (C) with the molar ratio of C to MgO . SiO2 equal to 6.0 was heated at 1250 degrees C for 7 h in nitrogen atmosphere. The crystalline phase of the carbothermally reduced powder was only MgSiN2. The residual carbon could be removed by heating the powder at 600 degrees C for 1 h in air. The yield of MgSiN2 powder was similar to 70%. The resulting powder contained 3.22 mol% oxygen. The primary particle sizes were ranging from 0.1 to 0.5 mu m.

Magnesium silicon nitride (MgSiN_2) was synthesized by the nitridation of powders in the magnesium (Mg) -silicon (Si) system. Although an Mg and Si powder with an Mg/Si ratio of 1.0 ( = stoichiometric ratio of MgSiN_2) was heated up to 1400℃ in nitrogen (N_2) , a single phase of MgSiN_2 could not be obtained, due to evaporation of Mg during heating. On the basis of the information that Mg_2Si formed as an intermediate phase during the synthesis of MgSiN_2, an Mg_2Si powder was heated at a temperature between 600 and 1600℃ for 1h in N_2. Although MgSiN_2 and other phases such as Si and amorphous Mg_3N_2 were present in the temperature range of 900℃ to 1300℃, the powder heated at 1400℃ consisted of only MgSiN_2 phase. The chemical composition of the powder heated at 1400℃ for 1h was almost stoichiometric; the content of the oxygen was as low as 0.76 mol%. The powder consisted of agglomerates with sizes of 〜5μm; these agglomerates were furthermore composed of primary particles with an average size of 0.54 μm. The oxidation resistant temperature of MgSiN_2 was estimated to be 〜830℃. The MgSiN_2 powder had good resistivity to hydration.