掺镁锰基钙钛矿的晶体结构与电磁性质
摘要
钙钛矿结构的稀土锰氧化物以其庞磁阻现象和自旋-电荷-轨道间的相互作用而产生的丰富物理内涵而备受瞩目。尽管人们已对此进行了大量研究，但目前对这类材料的深入认识以及庞磁阻效应机理的合理解释仍需作深入细致的研究。本论文以掺镁锰基钙钛矿为研究对象，比较系统的研究了镁的占位情况以及镁掺杂量对锰钙钛矿晶体结构，电性及磁性的影响，希望得到镁掺杂对钙钛矿电磁性质即相互作用机理作出合理的解释。
我们以简单钙钛矿为对象对镁的占位进行了研究。结果显示，镁既可以占据A位，也可以占据B位。虽然钙钛矿的A，B位对掺杂离子有较大的宽容度，但对于镁离子，占据A位的容忍因子仅为0．79-0．85；而占据B位的容忍因子为0．85-1．07，在镁的占位过程中，似乎热力学占据主导因素。
B位掺杂样品当掺杂量大于0．08时，低温磁性行为表现出自旋玻璃态，这和镁掺杂直接相关。非磁性镁离子的引入在样品中形成了竞争性的铁磁性和反铁磁性相，两相的竞争导致了自旋玻璃态的形成。
Mg掺杂明显影响MnO。八面体的面内弯曲振动模。掺杂浓度较高时，v4面内弯曲振动峰发生劈裂。Mg~(2+)在A位掺杂对v4面内弯曲振动的影响小于Mg~(2+)在B位掺杂的影响。对于v3伸缩振动，Mg在A或B位掺杂有相同的影响。
样品T>Tp时，B位掺杂样品的电阻符合阿仑尼乌斯公式。
样品的活化能随着Mg掺杂量的提高单调增大，外加磁场的增大相应的增大了活化能。
The discovery of magnetoresistance in metal multiplayer, magnetic tunneling junction and manganese perovskite oxides has aroused much attention recent years. Many works focus on the doped rare-earth manganate for their huge value of magnetoresistance and various magnetic and electric properties. However, there are still a lot of problems about the magnetoresistance mechanism which need to be clarified.
In this thesis, the main research focused on synthesis, characterization and investigation of the crystal structure, the magnetic and electrical properties of the cubic perovskite, double perovskite and layered perovskite manganate doped by magnesium in A-site or B-site. We hope to understand the action mechanism and influence factors on physical properties in the compounds family more clearly. The Mg-doped perovskite has not been well-studied so far. We took the cubic perovskite as an object to make a study on Mg-site.The result showed that Mg ions could take both A-site and B-site. In the case of A-site, pure La_(1-x)Mg_xMnO_3 could be gained when x<0.24 in atmosphere;MgMn_2O_4 was observed when x>0.33. In the case of B-site, the Mg-doped sample could be got only when x≤0.40 with the temperature above 1350℃.The value of tolerance factor (t) is only 0.79-0.85 in A-site and 0.85-1.07 in B-Site. It seems that thermodynamics plays a leading role in the synthesis process of the Mg-doped sample. The result shows that it is easier for the Mg-doped sample to form stable compounds in A-site which is twelve-liganded than in B-site which is eight-liganded. But when it comes to the layer-structured perovskite with Mg in both A-site and B-site, the Mg-dopde layered structure could not be obtained even at 1450℃.The experiment result of double perovskite is not ideal either, only the impure mixture obtained both under the condition of pure H_2 and H_2+Ar.It is considered that the Mg ions with high charge and small ion radius play an important role in the synthesis process.
We substituted Mg for Mn in the LaMnO_3 compound. LaMn_(1-x)Mg_xO_3 single phases can be were.formed up to x=0.5.Structural and electronic properties were studied by means of x-ray diffraction and SQUID. The samples with low Mg content showed a ferromagnetic state while samples with x>0.8 undergo a spin-glass transition at low temperatures. This implies the presence of competitive interaction between FM and AFM clusters. The spin-glass transition developed at lower temperatures as the Mn content decreased in agreement with a diminution of the number and size of magnetic clusters.
When x>0.08, doped sample showed spin-glass state. FM cluster and AFM cluster co-existed in the sample at low temperature. The competition of DE influence of FM with SE influence of AFM decided the character of the sample. It was in spin-glass state when Mn~(4+)/Mn~(3+)≥0.125 existed in B- site doped ions.
We investigated the IR spectrum of the samples and got the following results: the v_4 (vibration absorb peak ) of the MnO_6 octahedron was strongly changed by Mg-doped,and was split to two peaks when x≥0.24(A) or 0.28(B). the influence of Mg-doped in perovskite is slight to La_(1-x)Mg_xMnO_3 than LaMn_(1-x)Mg_xO_3.Mg dopant doesn't influence the wavenumbers of the v3 peak of the MnO_6 octahedron in La_(1-x)Mg_xMnO_3. The same phenomenon was observed when v3 peak was studied in LaMn_(1-x)Mg_xO_3
我们以简单钙钛矿为对象对镁的占位进行了研究。结果显示，镁既可以占据A位，也可以占据B位。虽然钙钛矿的A，B位对掺杂离子有较大的宽容度，但对于镁离子，占据A位的容忍因子仅为0．79-0．85；而占据B位的容忍因子为0．85-1．07，在镁的占位过程中，似乎热力学占据主导因素。
B位掺杂样品当掺杂量大于0．08时，低温磁性行为表现出自旋玻璃态，这和镁掺杂直接相关。非磁性镁离子的引入在样品中形成了竞争性的铁磁性和反铁磁性相，两相的竞争导致了自旋玻璃态的形成。
Mg掺杂明显影响MnO。八面体的面内弯曲振动模。掺杂浓度较高时，v4面内弯曲振动峰发生劈裂。Mg~(2+)在A位掺杂对v4面内弯曲振动的影响小于Mg~(2+)在B位掺杂的影响。对于v3伸缩振动，Mg在A或B位掺杂有相同的影响。
样品T>Tp时，B位掺杂样品的电阻符合阿仑尼乌斯公式。
样品的活化能随着Mg掺杂量的提高单调增大，外加磁场的增大相应的增大了活化能。
The discovery of magnetoresistance in metal multiplayer, magnetic tunneling junction and manganese perovskite oxides has aroused much attention recent years. Many works focus on the doped rare-earth manganate for their huge value of magnetoresistance and various magnetic and electric properties. However, there are still a lot of problems about the magnetoresistance mechanism which need to be clarified.
In this thesis, the main research focused on synthesis, characterization and investigation of the crystal structure, the magnetic and electrical properties of the cubic perovskite, double perovskite and layered perovskite manganate doped by magnesium in A-site or B-site. We hope to understand the action mechanism and influence factors on physical properties in the compounds family more clearly. The Mg-doped perovskite has not been well-studied so far. We took the cubic perovskite as an object to make a study on Mg-site.The result showed that Mg ions could take both A-site and B-site. In the case of A-site, pure La_(1-x)Mg_xMnO_3 could be gained when x<0.24 in atmosphere;MgMn_2O_4 was observed when x>0.33. In the case of B-site, the Mg-doped sample could be got only when x≤0.40 with the temperature above 1350℃.The value of tolerance factor (t) is only 0.79-0.85 in A-site and 0.85-1.07 in B-Site. It seems that thermodynamics plays a leading role in the synthesis process of the Mg-doped sample. The result shows that it is easier for the Mg-doped sample to form stable compounds in A-site which is twelve-liganded than in B-site which is eight-liganded. But when it comes to the layer-structured perovskite with Mg in both A-site and B-site, the Mg-dopde layered structure could not be obtained even at 1450℃.The experiment result of double perovskite is not ideal either, only the impure mixture obtained both under the condition of pure H_2 and H_2+Ar.It is considered that the Mg ions with high charge and small ion radius play an important role in the synthesis process.
We substituted Mg for Mn in the LaMnO_3 compound. LaMn_(1-x)Mg_xO_3 single phases can be were.formed up to x=0.5.Structural and electronic properties were studied by means of x-ray diffraction and SQUID. The samples with low Mg content showed a ferromagnetic state while samples with x>0.8 undergo a spin-glass transition at low temperatures. This implies the presence of competitive interaction between FM and AFM clusters. The spin-glass transition developed at lower temperatures as the Mn content decreased in agreement with a diminution of the number and size of magnetic clusters.
When x>0.08, doped sample showed spin-glass state. FM cluster and AFM cluster co-existed in the sample at low temperature. The competition of DE influence of FM with SE influence of AFM decided the character of the sample. It was in spin-glass state when Mn~(4+)/Mn~(3+)≥0.125 existed in B- site doped ions.
We investigated the IR spectrum of the samples and got the following results: the v_4 (vibration absorb peak ) of the MnO_6 octahedron was strongly changed by Mg-doped,and was split to two peaks when x≥0.24(A) or 0.28(B). the influence of Mg-doped in perovskite is slight to La_(1-x)Mg_xMnO_3 than LaMn_(1-x)Mg_xO_3.Mg dopant doesn't influence the wavenumbers of the v3 peak of the MnO_6 octahedron in La_(1-x)Mg_xMnO_3. The same phenomenon was observed when v3 peak was studied in LaMn_(1-x)Mg_xO_3
引文
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