Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly emplo...Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly employed in calculations.However, the choice of the Hubbard U parameter has been a subject of debate and its value has been reported over a wide range. In this paper, taking focus on the phase transition behavior of VO_(2), the Hubbard U parameter for vanadium oxide is determined by using the quasi-harmonic approximation(QHA). First-principles calculations demonstrate that the phase transition temperature can be modulated by varying the U values. The phase transition temperature can be well reproduced by the calculations using the Perdew–Burke–Ernzerhof functional combined with the U parameter of 1.5eV. Additionally,the calculated band structure, insulating or metallic properties, and phonon dispersion with this U value are in line with experimental observations. By employing the QHA to determine the Hubbard U parameter, this study provides valuable insights into the phase transition behavior of VO_(2). The findings highlight the importance of electron correlation effects in accurately describing the properties of this material. The agreement between the calculated results and experimental observations further validates the chosen U value and supports the use of the DFT+U method in studying VO_(2).展开更多
We employed ab-initio calculations to investigate the structural and thermodynamic properties of Massicot or orthorhombic phase of PbO named β-PbO using the projector augmented-wave（PAW） method within the generaliz...We employed ab-initio calculations to investigate the structural and thermodynamic properties of Massicot or orthorhombic phase of PbO named β-PbO using the projector augmented-wave（PAW） method within the generalized gradient approximation（GGA）. The temperature and pressure dependence of bulk modulus, heat capacity at constant pressure and constant volume, entropy, thermal expansion coefficient and Grüneisen parameter were discussed. Accuracy of two different models, the Debye and Debye-Grüneisen which are based on the quasi-harmonic approximation（QHA） for producing thermodynamic properties of material were compared. According to calculation results, these two models can be used to designate thermodynamic properties for β-PbO with sensible accuracy over a wide range of temperatures and pressures, and our work on the properties of this structure will be useful for more deeply understanding various properties of this structure.展开更多
GaTe is a two-dimensional Ⅲ-Ⅵ semiconductor with suitable direct bandgap of~1.65 eV and high photoresponsivity,which makes it a promising candidate for optoelectronic applications.GaTe exists in two crystalline phas...GaTe is a two-dimensional Ⅲ-Ⅵ semiconductor with suitable direct bandgap of~1.65 eV and high photoresponsivity,which makes it a promising candidate for optoelectronic applications.GaTe exists in two crystalline phases:monoclinic(m-GaTe,with space group C2/m) and hexagonal(h-GaTe,with space group P63/mmc).The phase transition between the two phases was reported under temperature-varying conditions,such as annealing,laser irradiation,etc.The explicit phase transition temperature and energy barrier during the temperature-induced phase transition have not been explored.In this work,we present a comprehensive study of the phase transition process by using first-principles energetic and phonon calculations within the quasi-harmonic approximation framework.We predicted that the phase transition from h-GaTe to m-GaTe occurs at the temperature decreasing to 261 K.This is in qualitative agreement with the experimental observations.It is a two-step transition process with energy barriers 199 meV and 288 meV,respectively.The relatively high energy barriers demonstrate the irreversible nature of the phase transition.The electronic and phonon properties of the two phases were further investigated by comparison with available experimental and theoretical results.Our results provide insightful understanding on the process of temperature-induced phase transition of GaTe.展开更多
The internal mechanisms of nucleation and growth of L1_(2)-AI_(3)RE(RE=Sc,Y,La-Lu) second phases in Al alloys were investigated by combining first-principles calculations with quasi-harmonic approximation(QHA).The cal...The internal mechanisms of nucleation and growth of L1_(2)-AI_(3)RE(RE=Sc,Y,La-Lu) second phases in Al alloys were investigated by combining first-principles calculations with quasi-harmonic approximation(QHA).The calculated results show that the diffusion rate D_s and chemical potential AG_V increase with the increase of temperature.With the increase of atomic number,the D_s and the strain energy ΔE_(CS)increase firstly from Sc to La,and then decreases,while the calculated interface energy γ_(α/β) and ΔG_V show opposite tendency.Based on above calculated results,the critical nucleation radius R*and coarsening rate K_(LSW) are obtained from the classical nucleation theory(CNT) and LSW model of the Ostwald ripening of particles,respectively.With the increase of atomic number,the R*increases firstly,and then decreases for all planes at finite temperatures.Whereas the K_(LSW) shows opposite variation to the R^(*).From this point of view,it is reasonably speculated that Y and later RE elements can replace the expensive Sc for heat-resistance Al alloys.The solubility c_(∞) of particles is usually very small at low temperature,and there is obvious solubility only when the temperature reaches 600 K.The surface energies E_(sur) of AI_(3)RE compounds and Al solid solution are respectively larger and smaller than that of pure Al,respectively,except for the surface(001) and(110) of Al_(3)La.For all planes,with the increase of atomic number of RE,E_(sur) decreases firstly from Sc to La,and then increases linearly to Lu.These results are helpful for designing high performance heat-resistance Al alloys.展开更多
321 phases are an atypical series of MAX phases,in which A=As/P,with superior elastic properties,fea-turing in the MA-triangular-prism bilayers in the crystal structure.Until now,besides Nb 3 As 2 C,the pure phases of...321 phases are an atypical series of MAX phases,in which A=As/P,with superior elastic properties,fea-turing in the MA-triangular-prism bilayers in the crystal structure.Until now,besides Nb 3 As 2 C,the pure phases of the other 321 compounds have not been realized,hampering the study of their intrinsic prop-erties.Here,molten-salt sintering(MSS)and solid-state synthesis(SSS)were applied to synthesize As/P-containing 321 phases and 211 phases.Analyzing the phase composition of the end-product via multiple-phase Rietveld refinement,we found that MSS can effectively improve the purity of P-containing MAX phases,with the phase content up to 99%in Nb_(3)P_(2)C and 75.4(5)%in Nb 2 PC.In contrast,MSS performed poorly on As-containing MAX phases,only 8.9(4)%for Nb 3 As 2 C and 64(2)%for Nb 2 AsC,as opposed to the pure phases obtained by SSS.The experimental analyses combined with first-principles calculations reveal that the dominant formation route of Nb_(3)P_(2)C is through NbP+Nb+C→Nb_(3)P_(2)C.Moreover,we found that the benefits of MSS on P-containing MAX phases are on the facilitation of three consid-ered chemical reaction routes,especially on Nb 2 PC+NbP→Nb_(3)P_(2)C.Furthermore,the intrinsic physical properties and Fermi surface topology of two 321 phases consisting of electron,hole,and open orbits are revealed theoretically and experimentally,in which the electron carriers are dominant in electrical trans-port.The feasible synthesis methods and the formation mechanism are instructive to obtain high-purity As/P-containing MAX phases and explore new MAX phases.Meanwhile,the intrinsic physical properties will give great support for future applications on 321 phases.展开更多
基金supported by the National Natural Science Foundation of China (Grant Nos.21933006 and 21773124)the Fundamental Research Funds for the Central Universities Nankai University (Grant Nos.010-63233001,63221346,63213042,and ZB22000103)+1 种基金the support from the China Postdoctoral Science Foundation (Grant No.2021M691674)the Hefei National Laboratory for Physical Sciences at the Microscale (Grant No.KF2020105)。
文摘Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly employed in calculations.However, the choice of the Hubbard U parameter has been a subject of debate and its value has been reported over a wide range. In this paper, taking focus on the phase transition behavior of VO_(2), the Hubbard U parameter for vanadium oxide is determined by using the quasi-harmonic approximation(QHA). First-principles calculations demonstrate that the phase transition temperature can be modulated by varying the U values. The phase transition temperature can be well reproduced by the calculations using the Perdew–Burke–Ernzerhof functional combined with the U parameter of 1.5eV. Additionally,the calculated band structure, insulating or metallic properties, and phonon dispersion with this U value are in line with experimental observations. By employing the QHA to determine the Hubbard U parameter, this study provides valuable insights into the phase transition behavior of VO_(2). The findings highlight the importance of electron correlation effects in accurately describing the properties of this material. The agreement between the calculated results and experimental observations further validates the chosen U value and supports the use of the DFT+U method in studying VO_(2).
基金Project supported by the Research Project of Islamic Azad University,Urmia Branch
文摘We employed ab-initio calculations to investigate the structural and thermodynamic properties of Massicot or orthorhombic phase of PbO named β-PbO using the projector augmented-wave（PAW） method within the generalized gradient approximation（GGA）. The temperature and pressure dependence of bulk modulus, heat capacity at constant pressure and constant volume, entropy, thermal expansion coefficient and Grüneisen parameter were discussed. Accuracy of two different models, the Debye and Debye-Grüneisen which are based on the quasi-harmonic approximation（QHA） for producing thermodynamic properties of material were compared. According to calculation results, these two models can be used to designate thermodynamic properties for β-PbO with sensible accuracy over a wide range of temperatures and pressures, and our work on the properties of this structure will be useful for more deeply understanding various properties of this structure.
基金Project supported by the National Natural Science Foundation of China(Grant No.62004080)Postdoctoral Innovative Talents Supporting Program(Grant No.BX20190143)+1 种基金China Postdoctoral Science Foundation(2020M670834)Jilin Province Science and Technology Development Program,China(Grant No.20190201016JC)。
文摘GaTe is a two-dimensional Ⅲ-Ⅵ semiconductor with suitable direct bandgap of~1.65 eV and high photoresponsivity,which makes it a promising candidate for optoelectronic applications.GaTe exists in two crystalline phases:monoclinic(m-GaTe,with space group C2/m) and hexagonal(h-GaTe,with space group P63/mmc).The phase transition between the two phases was reported under temperature-varying conditions,such as annealing,laser irradiation,etc.The explicit phase transition temperature and energy barrier during the temperature-induced phase transition have not been explored.In this work,we present a comprehensive study of the phase transition process by using first-principles energetic and phonon calculations within the quasi-harmonic approximation framework.We predicted that the phase transition from h-GaTe to m-GaTe occurs at the temperature decreasing to 261 K.This is in qualitative agreement with the experimental observations.It is a two-step transition process with energy barriers 199 meV and 288 meV,respectively.The relatively high energy barriers demonstrate the irreversible nature of the phase transition.The electronic and phonon properties of the two phases were further investigated by comparison with available experimental and theoretical results.Our results provide insightful understanding on the process of temperature-induced phase transition of GaTe.
基金Project supported by the R&D plan for Key Areas in Guangdong Province (2020B010186001)the National Natural Science Foundation of China (52171115,52071299)。
文摘The internal mechanisms of nucleation and growth of L1_(2)-AI_(3)RE(RE=Sc,Y,La-Lu) second phases in Al alloys were investigated by combining first-principles calculations with quasi-harmonic approximation(QHA).The calculated results show that the diffusion rate D_s and chemical potential AG_V increase with the increase of temperature.With the increase of atomic number,the D_s and the strain energy ΔE_(CS)increase firstly from Sc to La,and then decreases,while the calculated interface energy γ_(α/β) and ΔG_V show opposite tendency.Based on above calculated results,the critical nucleation radius R*and coarsening rate K_(LSW) are obtained from the classical nucleation theory(CNT) and LSW model of the Ostwald ripening of particles,respectively.With the increase of atomic number,the R*increases firstly,and then decreases for all planes at finite temperatures.Whereas the K_(LSW) shows opposite variation to the R^(*).From this point of view,it is reasonably speculated that Y and later RE elements can replace the expensive Sc for heat-resistance Al alloys.The solubility c_(∞) of particles is usually very small at low temperature,and there is obvious solubility only when the temperature reaches 600 K.The surface energies E_(sur) of AI_(3)RE compounds and Al solid solution are respectively larger and smaller than that of pure Al,respectively,except for the surface(001) and(110) of Al_(3)La.For all planes,with the increase of atomic number of RE,E_(sur) decreases firstly from Sc to La,and then increases linearly to Lu.These results are helpful for designing high performance heat-resistance Al alloys.
基金supported by the National Science Foundation for Young Scientists of China(No.51902055)the Natural Science Foundation of Fujian Province(Nos.2021J011077,2021J05224,and 2020J01898).
文摘321 phases are an atypical series of MAX phases,in which A=As/P,with superior elastic properties,fea-turing in the MA-triangular-prism bilayers in the crystal structure.Until now,besides Nb 3 As 2 C,the pure phases of the other 321 compounds have not been realized,hampering the study of their intrinsic prop-erties.Here,molten-salt sintering(MSS)and solid-state synthesis(SSS)were applied to synthesize As/P-containing 321 phases and 211 phases.Analyzing the phase composition of the end-product via multiple-phase Rietveld refinement,we found that MSS can effectively improve the purity of P-containing MAX phases,with the phase content up to 99%in Nb_(3)P_(2)C and 75.4(5)%in Nb 2 PC.In contrast,MSS performed poorly on As-containing MAX phases,only 8.9(4)%for Nb 3 As 2 C and 64(2)%for Nb 2 AsC,as opposed to the pure phases obtained by SSS.The experimental analyses combined with first-principles calculations reveal that the dominant formation route of Nb_(3)P_(2)C is through NbP+Nb+C→Nb_(3)P_(2)C.Moreover,we found that the benefits of MSS on P-containing MAX phases are on the facilitation of three consid-ered chemical reaction routes,especially on Nb 2 PC+NbP→Nb_(3)P_(2)C.Furthermore,the intrinsic physical properties and Fermi surface topology of two 321 phases consisting of electron,hole,and open orbits are revealed theoretically and experimentally,in which the electron carriers are dominant in electrical trans-port.The feasible synthesis methods and the formation mechanism are instructive to obtain high-purity As/P-containing MAX phases and explore new MAX phases.Meanwhile,the intrinsic physical properties will give great support for future applications on 321 phases.
