γ-Si3N4在高压下的电子结构和物理性质研究

采用基于密度泛函平面波赝势方法(PWP)和广义梯度近似(GGA-PW91),计算了不同压强下γ-Si3N4的电子结构、光学性质和力学性质.基于计算结果,分析讨论了γ-Si3N4各物理参数随外压力的变化规律.计算表明,γ-Si3N4是一种适合于在高压条件下工作的材料.     

Si(111)表面在NH3气氛下形成Si3N4薄膜的STM研究

利用扫描隧道显微镜(STM)对Si(111)在氨气气氛下进行氮化所获得的氮化硅薄膜形貌和表面结构进行了系统分析,结果表明在1075-1275 K的温度下对Si(111)进行氮化可以获得较平整的晶态β-Si3N4薄膜,并在氮化膜表面观察到了Si3N4(0001)表面的(4×4)再构.     

β-Si3N4电子结构和红外和拉曼频率的第一性原理研究

分别用PW91,B3LYP两种密度泛函方法和全电子高斯基组对β-Si3N4的几何结构进行全优化(包括晶格参数和原子坐标),结果和实验值符合良好. 同时计算了能带结构和态密度. 在此基础上分别用上述两种方法计算了Γ点拉曼振动频率,并按对称性进行分类,将得到的11种拉曼活性模式的频率值与实验值以及其他文献值进行了比较,进一步确定了Ag模式为中等频率,值约459cm-1. 计算结果表明,B3LYP总体计算结果优于PW91. 对于中低频段的拉曼频率,两者与实验值相差最大为2和17cm-1. 对于高频段,两者与实验值相差最大为16和35cm-1. 同时计算了β-Si3N4的Γ点红外振动频率,通过对比实验结果,将其红外光谱进行了归属.     

Pressure-induced phase transition in silicon nitride material

The equilibrium crystal structures,lattice parameters,elastic constants,and elastic moduli of the polymorphs α-,β-,and γ-Si3N4,have been calculated by first-principles method.β-Si3N4 is ductile in nature and has an ionic bonding.γSi3N4 is found to be a brittle material and has covalent chemical bonds,especially at high pressures.The phase boundary of the β→γ transition is obtained and a positive slope is found.This indicates that at higher temperatures it requires higher pressures to synthesize γ-Si3N4.On the other hand,the α→γ phase boundary can be described as P = 14.37198+ 3.27 × 10?3T-7.83911 × 10?7T2-3.13552 × 10?10T3.The phase transition from α-to γ-Si3N4 occurs at 16.1 GPa and 1700 K.Then,the dependencies of bulk modulus,heat capacity,and thermal expansion on the pressure P are obtained in the ranges of 0 GPa-30 GPa and 0 K-2000 K.Significant features in these properties are observed at high temperatures.It turns out that the thermal expansion of γ-Si3N4 is larger than that of α-Si3N4 over wide pressure and temperature ranges.The evolutions of the heat capacity with temperature for the Si3N4 polymorphs are close to each other,which are important for possible applications of Si3N4.     

立方氮化硅的冲击波合成实验

氮化硅在常态下的两种已知物相（α和β相）均为六方结构，最近新发现第3种具有立方尖晶石结构的氮化硅（以下称立方氮化硅或γ-Si3N4）可通过高温高压条件合成得到，是继金刚石、立方氮化硼之后的又一种超硬材料。各国学者在合成立方氮化硅的研究中开展了积极的工作，然而，目前所用的技术手段仅能合成出极少量的γ-Si3N4粉体样品，无法进一步开展其块体材料的研究，并制约了该新材料在工业技术中的应用。     

Predictions of pressure-induced structural transition,mechanical and thermodynamic properties of α-and β-Si₃N₄ ceramics:ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4.The ground-state parameters accord quite well with the experimental data.Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K.The α→β phase transformation would not occur in a pressure range of 0-40 GPa and a temperature range of 0-300 K.Actually,the α→β transition occurs at 1600 K and 7.98 GPa.For α-and β-Si3N4,the c axes are slightly more incompressible than the a axes.We conclude that β-Si3N4 is a hard material and ductile in nature.On the other hand,β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0-10 GPa.Besides,the thermodynamic properties such as entropy,heat capacity,and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures.Significant features in these properties are observed at high temperature.The calculated results are in good agreement with available experimental data and previous theoretical values.Many fundamental solid-state properties are reported at high pressure and high temperature.Therefore,our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

Predictions of pressure-induced structural transition, mechanical and thermodynamic properties of α-and β-Si3N4 ceramics: ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4.The ground-state parameters accord quite well with the experimental data.Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K.The α→β phase transformation would not occur in a pressure range of 0-40 GPa and a temperature range of 0-300 K.Actually,the α→β transition occurs at 1600 K and 7.98 GPa.For α-and β-Si3N4,the c axes are slightly more incompressible than the a axes.We conclude that β-Si3N4 is a hard material and ductile in nature.On the other hand,β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0-10 GPa.Besides,the thermodynamic properties such as entropy,heat capacity,and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures.Significant features in these properties are observed at high temperature.The calculated results are in good agreement with available experimental data and previous theoretical values.Many fundamental solid-state properties are reported at high pressure and high temperature.Therefore,our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

β-C3N4,β-Si3N4和β-Ge3N4的能带结构

采用基于密度泛函理论的线性丸盒轨道原子球近似(LMTO-ASA)从头计算方法,研究了β-C₃N₄,β-Si₃N₄和β-Ge₃N₄的能带结构,得到了它们的能隙分别为:4.1751,5.1788和4.0279eV。对于β-C₃N₄,由于N的部分2p电子占据了非键轨道,禁带宽度较窄;对于β-Si₃N_{4关键词：}     

mechanical and thermodynamic properties of α-and β-Si3N4 ceramics： ab initio and quasi-harmonic Debye modeling

The plane-wave pseudo-potential method within the framework of ab initio technique is used to investigate the structural and elastic properties of α-and β-Si3N4. The ground-state parameters accord quite well with the experimental data. Our calculation reveals that α-Si3N4 can retain its stability to at least 40 GPa when compressed at 300 K. The α → β phase transformation would not occur in a pressure range of 0-40 （3Pa and a temperature range of 0 300 K. Actually, the α → β transition occurs at 1600 K and 7.98 GPa. For α-and β-Si3N4, the c axes are slightly more incompressible than the a axes. We conclude that β-Si3N4 is a hard material and ductile in nature. On the other hand, β-Si3N4 is also found to be an ionic material and can retain its mechanical stability in a pressure range of 0 - 010 GPa. Besides, the thermodynamic properties such as entropy, heat capacity, and Debye temperature of α-and β-Si3N4 are determined at various temperatures and pressures. Significant features in these properties are observed at high temperature. The calculated results are in good agreement with available experimental data and previous theoretical values. Many fundamental solid-state properties are reported at high pressure and high temperature. Therefore, our results may provide useful information for theoretical and experimental investigations of the Si3N4 polymorphs.     

掺稀土元素(Y,La)的γ-Si3N4的电子结构和光学性质

采用基于密度泛函的平面赝势方法(PWP)和广义梯度近似(GGA),计算了未掺杂和掺杂稀土(Y,La)的γ-Si3N4中N-Y(La)键的布居值和它们的键长、掺杂后能带结构和态密度.发现掺杂后的带隙要减小,并且可能形成新的半导体,这将为找到新的半导体提供一个方向.还进一步研究了掺杂稀土(Y,La)后的光学性质,掺杂后有更高的静态介电常数,可以作为新的介电材料和好的折射材料,这对于一定的光学元件有潜在的应用前景.     

The effects of radiation damage on power VDMOS devices with composite SiO2-Si3N4 films

Total dose effects and single event effects on radiation-hardened power vertical double-diffusion metal oxide semiconductor(VDMOS) devices with composite SiO2-Si3N4 film gates are investigated.The relationships among the important electrical parameters of the samples with different thickness SiO2-Si3N4 films,such as threshold voltage,breakdown voltage,and on-state resistance in accumulated dose,are discussed.The total dose experiment results show that the breakdown voltage and the on-state resistance barely change with the accumulated dose.However,the relationships between the threshold voltages of the samples and the accumulated dose are more complex,and not only positively drift,but also negatively drift.At the end of the total dose experiment,we select the group of samples which have the smaller threshold voltage shift to carry out the single event effect studies.We find that the samples with appropriate thickness ratio SiO2-Si3N4 films have a good radiation-hardening ability.This method may be useful in solving both the SEGR and the total dose problems with the composite SiO2-Si3N4 films.     

从头计算对GanNm团簇的结构与稳定性的研究

用B3LYP-DFT方法对GanN2(n=1~7)和GanN(n=2~8)团簇的结构与稳定性进行了研究.在6-31G*水平上进行了结构优化和频率分析,得到了GanN2(n=1~7)和GanN(n=2~8)团簇的基态结构.在GanN(n=2~8)团簇的基态几何结构中,N原子处在分子结构的中心;在GanN2(n=1~3)团簇中,N—N键比Ga—N键强;在GanN2(n=4~7)团簇中存在Ga3N单元和Ga4N单元.在GanN2(n=1~7)和GanN(n=2~8)团簇中,Ga4N2,Ga6P2,Ga3N,Ga5N和Ga7N较其它团簇稳定.     

β-Si3N4电子结构和光学性质的第一性原理研究

采用基于密度泛函的平面波赝势方法(PWP)和广义梯度近似(GGA)，计算了β相氮化硅(β-Si₃N₄)的电子结构和光学性质，得到的晶格常数、能带结构等均与实验结果较好符合.进一步还研究了β-Si₃N₄的光吸收系数以及禁带宽度随外压力的变化规律，为β-Si₃N₄材料在高压条件下的应用提供了理论参考. 关键词： β相氮化硅 电子结构 能带结构 光学性质     

微波等离子体化学气相沉积法制备C3N4薄膜的结构研究

采用微波等离子体化学气相沉积法,用高纯氮气（99．999％）和甲烷（99．9％）作反应气体,在单晶Si(100)基片上沉积C3N4薄膜,利用扫描电子显微镜观察薄膜形貌,表明薄膜由密排的六棱晶棒组成,X射线衍射和透射电子显微镜结构分析说明该薄膜主要由β－C3N4和α－C3N4组成,并且这些结果与a-C3N4相符合较好,由虎克定律近似关系式计算了α－和β－C3N4的傅里叶变换红外光谱和Raman光谱,实验结果支持C－N共价键的存在。     

Investigations of high-pressure and high-temperature behaviors of the newly-discovered willemite-Ⅱ and post-phenacite silicon nitrides

Using the first-principles method of the plane-wave pseudo-potential, the structural properties of the newly-discovered willemite-Ⅱ Si3N4 （wⅡ phase） and post-phenacite Si3N4 （δ phase） are investigated. The α phase is predicted to undergo a first-order α→wⅡ phase transition at 18.6 GPa and 300 K. Within the quasi-harmonic approximation （QHA）, the α→wⅡ phase boundary is also obtained. When the well-known β→γ transition is suppressed by some kinetic reasons, the β→δ phase transformation could be observed in the phase diagram. Besides, the temperature dependences of the cell volume,thermal expansion coefficient, bulk modulus, specific heat, entropy and Debye temperature of the involved phases are determined from the non-equilibrium free energies. The thermal expansion coefficients of wⅡ-Si3N4 show no negative values in a pressure range of 0-30 GPa, which implies that the wⅡ-Si3N4 is mechanically stable. More importantly, the δ-Si3N4 is found to be a negative thermal expansion material. Further experimental investigations may be required to determine the physical properties of wⅡ- and δ-Si3N4 with higher reliability.     

Si_4N_4团簇结构与性质的密度泛函理论研究(英文)

用密度泛函理论(DFT)中的杂化密度泛函B3LYP方法,在6-31G(d)的水平上对Si4N4团簇的可能结构进行了几何结构优化和电子结构计算,得到了可能的17个异构体.Si4N4团簇的最稳定结构是有8个Si-N键的平面结构.用自然键轨道(NBO)方法分析了成键性质.计算结果表明,Si-N键中Si原子向N原子有较大的电荷转移,因此Si-N原子间有较强的电相互作用;最强的IR和Raman谱峰分别位于1387.64cm-1和1415.05cm-1处;并计算了Si4N4团簇的最稳定结构的极化率和超极化率.     

Si3N4团簇结构与性质的密度泛函理论研究

用杂化密度泛函B3LYP在6-31G*的水平上研究了Si3N4团簇可能结构的平衡几何构型和电子结构,得到了24个可能的异构体.Si3N4团簇的最稳定结构是由7个Si—N键和2个N—N键形成的3个四边形构成的三维结构.用自然键轨道方法(NBO)分析了成键性质,结果表明,Si—N键中的Si、N原子的净电荷较大,说明Si—N键中Si、N原子的相互作用主要是电相互作用.最强的IR和Raman峰分别位于1033.40 cm-1,473.63 cm-1处.并且讨论了最稳定结构的极化率和超极化率.     

氮化硅新相P6和P6'的理论研究：一种研究陶瓷材料的新工具

在原子尺度上构建模型,采用密度泛函理论结合准谐波近似研究了氮化硅新相(P6和P6'相)的点阵常数、弹性常数和弹性模量. 并使用β-Si₃N₄作基准材料来测试计算结果的准确性. 研究发现β-Si3N4的晶胞常数和弹性常数与实验值吻合相当好. 研究了P6和P6'相在30～55 GPa的各向异性因子、脆性和力学稳定性,结果表明两相属于金属性和脆性材料,且晶体的脆性和各向异性都随着压强的升高而增大. β相在40 GPa和300 K时会转变成P6'相. 当压强继续升高到5     

Si(111)表面在NH3气氛下形成Si3N4薄膜的STM研究

利用扫描隧道显微镜(STM)对Si(111)在氨气气氛下进行氮化所获得的氮化硅薄膜形貌和表面结构进行了系统分析,结果表明在1075—1275K的温度下对Si(111)进行氮化可以获得较平整的晶态βSi3N4薄膜,并在氮化膜表面观察到了Si3N4(0001)表面的(4×4)再构. 关键词：     

含氮氟化类金刚石(FN-DLC)薄膜的研究：(Ⅳ)氮掺杂对薄膜结构的影响

不同条件下，在单晶硅基片上沉积了含氮氟化类金刚石(FN-DLC)薄膜.原子力显微(AFM)形貌显示，掺N后，薄膜变得致密均匀.傅里叶变换吸收红外光谱(FTIR)表明，随着r(r=N₂/［N₂+CF₄+CH₄］)的增大薄膜中C—H键的逐渐减少，C〖FY=,1〗N和C≡N键含量逐渐增加.X射线光电子能谱(XPS)的C1s和N1s峰拟合结果发现，N掺入导致在薄膜中出现β-C₃N₄和a-CN_x(x=1,2,3)成分.Roman散射谱的G峰向高频方向位移和峰值展宽等证明：随着r的增大，薄膜内sp²键态含量增加. 关键词： 氟化类金刚石膜 键结构 氮掺杂