钙钛矿结构La_(2/3-x)Y_xCa_(1/3)MnO_3的制备以及拉曼与红外光谱分析
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摘要
因为巨磁阻效应的发现,具有钙钛矿结构的锰氧化物La1-xCaxMnO3受人们的广泛关注。因为其中的电子轨道,自旋,电荷,晶格之间的复杂的相互作用,这类材料表现出丰富的物理现象,如金属-绝缘体的转变、电相分离、磁转变和电荷有序态等现象。巨磁电阻锰氧化物是在母体化合物LaMnO3的La位置上进行三价或二价元素掺杂而形成的。如La1-yRyRexMnO3锰氧化物(R为三价稀土元素,如Y,Pr和Nd等；Re为二价碱土元素,如Ca, Sr和Ba等),以得到不同价态的Mn离子,从而改变母体化合物的晶体结构、电磁性质等,甚至导致微纳米尺度上的本征不均匀性。微观尺度上的不均匀性必然会导致材料广义介电常数和磁化率的不均匀性,它会对入射光的吸收系数和反射系数造成显著的变化,导致不同频率下的光的透射和反射强度随频率和空间位置的不同而发生变化。对比材料内部不同区域的微观尺度上的光谱可以揭示材料内部不同区域的电子跃迁、声子行为、元激发、电声子相互作用等复杂的物理过程的不同点。通过一定的处理方法,便可以直接显示微观不均匀性的图像。由于新型窄带关联电子材料的带隙和声子振动在红外波段,所以研究其红外光学性质对于深入理解其电子—声子相互作用,带内(间)电子跃迁,磁性随温度演化等众多的元激发过程尤为重要。
本文采用固相反应法制备了La2/3-xCa1/3MnO3(x=0,0.07,0.1,0.14)系列样品。对其晶体结构和电子输运特性、变温中红外光谱和激光显微共聚焦散射拉曼光谱进行了测试、表征和分析。论文结构如下：
第一章对锰氧化物的晶体结构、电磁特性、表征手段和选题意义进行了叙述。
第二章着重介绍了La2/3-xYrCa1/3MnO3(x=0,0.07,0.1,0.14)系列样品的制备过程和红外、拉曼光谱的实验原理及实验装置。
第三章,测量了样品的X射线衍射,对样品结构进行了研究。观测到随着Y掺杂的增多,四种样品的特征衍射峰向高角度逐渐移动。在75K300K的范围内采用四探针法来测试了样品的电阻率随温度变化的曲线。对于低掺杂的样品,其电阻率随温度的变化曲线显示它们在一些特定温度发生了由低温下的金属性导电到高温下半导体导电行为的转变。当Y掺杂较高时,这种转变消失,样品完全为绝缘体。在H=10Oe外加磁场下,用SQUID(超导量子干涉仪)测量了样品的磁性质。发现铁磁转变温度(即居里温度Tc)会随掺杂量Y的增加而明显减小。当掺杂量Y达到X=0.14时,样品不再呈现出顺磁—铁磁的转变,取而代之的是一种顺磁至反铁磁的转变过程。
第四章和第五章,对样品的红外光学和拉曼光谱进行了研究。对于未掺杂的样品(x=0),高温区域其远红外反射光谱很明显呈现出四个特征峰；但其中两个峰会随着温度的降低逐渐消失。高温下,特征峰的峰位会随温度的降低在铁磁的转变温度处呈现出很大变化。而对于掺杂Y的样品,这四个远红外反射光谱特征峰一直很明显的保持,不会随温度发生变化,尽管在磁性测量研究中表明掺杂Y的样品也会有明显的磁转变行为。但在中红外反射谱中Y掺杂样品在其磁转变温度附近发现很明显的转变。结合Mn06晶格振动模式和Jahn-Teller效应,可以对结果给出了定性解释。每种样品在激光拉曼光谱上都呈现出高波数峰(～610cm-1)、中波数峰(～450cm-1)和低波数峰(-220cm-1)三个明显的特征峰。但其中三个样品峰随温度变化没有较为明显的规律性。
Manganese oxide La1-xCaxMnO3with perovskite structure are paid great attention due to the discovery of colossal magnetoresistive effect inside. The complex interactions among the charge, orbital, spin and lattice give rise to the abundant physics properties, such as metal-insulator transition, magnetic transition, charge-ordering and phase separation. Manganese oxides like La1-yRyRexMnO3(R: rare earth elements Y, Prand Nd ect. with trivalence; Re:alkali elements Ca, Srand Ba ect. with double valence) are deduced from a matrix compound LaMnO3by doping on La sites, resulting in Mn ions with different valences, and consequently changing the crystal structure, electronic and magnetic properties of the matrix, and even intrinsic inhomogeneity at microscale. The inhomogeneity at microscale will inevitably induce the inhomogeneity of dielectric constant and magnetic susceptibility, which can be sensed by its far-infrared spectra. The spectra are sensitive to the vibration modes that are closely related to the electron-photo interaction, electron transition between interbands or intrabands and magnetic transitions.
The Y-doped manganese oxides La2/3-xYxCa1/3Mn03(x=0,0.07,0.1, and0.14) were sintered by a solid-state method. Their crystal structures, magnetic and electronic transport properties, reflectivity of mid/far infrared radiation spectra, and laser confocal microscopic Raman spectra were checked and characterized. The whole thesis is arranged as follow.
In chapter one, a brief introduction on the crystal structures, electro-magnetic properties, characterization methods of manganites and the aim of the thesis was expressed.
In chapter two, much attention was paid to the preparation of La2/3-xYxCai/3Mno3(X=0,0.07,0.1, and0.14) and the experimental setup of infrared and laser confocal microscopic Raman spectra analysis.
In chapter three, a X-ray diffractionmeter was employed to analyze structure of=0,0.07,0.1, and0.14). The resistivity of the samples were detected by a four-probe method from75K-300K; for lower doping-level samples, is was found a metallic state at low temperature and insulator-like conducting state at high temperature. And the transition temperature moves towards lower temperature with Y doping and the transition even disappears at x=0.14, in which the sample only shows an insulating behavior. The diffraction peaks move to the high angle for the four samples with Y increasing. The magnetic properties of these manganese La2/3-xYxCa1/3MnO3(x=0,0.07,0.1, and0.14) were checked with a SQUID under H=10Oe. It was found that ferromagnetic transition temperature (i.e. the Curie temperature Tc) decrease significantly with incensement of Y doping. When the doping level x=0.14, the sample does not show the paramagnetic to ferromagnetic transition, replaced by a paramagnetic to antiferromagnetic transition instead.
In chapter five, the infrared optical properties and Raman spectra of the samples were shown. For the undoped sample, four characteristic peaks in the far infrared radiation spectrum can be found at high temperatures and with the decrease of temperature two of them gradually fade away. The peak positions show a great change around the magnetic transition temperature of the sample. For the Y-doped samples, the four peaks become clearer. Although their magnetic properties also show sharp changes, the shape of the four peaks is stable and almost independent of temperature. However, there is a manifest change in the mid infrared radiation spectrum around the magnetic transitions. A qualitative explanation was proposed for the above results by taking the lattice vibration modes of Jahn-Teller effect in the Mn-o octahedral lattice into consideration. Three obvious characteristic peaks, high wave number peaks (～610cm-1), medium wave number peaks (～450cm-1) and low wave number peaks (～220cm-1), appear in Raman spectrum for each sample.But the other three peaks show no obvious changes with temperature.
本文采用固相反应法制备了La2/3-xCa1/3MnO3(x=0,0.07,0.1,0.14)系列样品。对其晶体结构和电子输运特性、变温中红外光谱和激光显微共聚焦散射拉曼光谱进行了测试、表征和分析。论文结构如下：
第一章对锰氧化物的晶体结构、电磁特性、表征手段和选题意义进行了叙述。
第二章着重介绍了La2/3-xYrCa1/3MnO3(x=0,0.07,0.1,0.14)系列样品的制备过程和红外、拉曼光谱的实验原理及实验装置。
第三章,测量了样品的X射线衍射,对样品结构进行了研究。观测到随着Y掺杂的增多,四种样品的特征衍射峰向高角度逐渐移动。在75K300K的范围内采用四探针法来测试了样品的电阻率随温度变化的曲线。对于低掺杂的样品,其电阻率随温度的变化曲线显示它们在一些特定温度发生了由低温下的金属性导电到高温下半导体导电行为的转变。当Y掺杂较高时,这种转变消失,样品完全为绝缘体。在H=10Oe外加磁场下,用SQUID(超导量子干涉仪)测量了样品的磁性质。发现铁磁转变温度(即居里温度Tc)会随掺杂量Y的增加而明显减小。当掺杂量Y达到X=0.14时,样品不再呈现出顺磁—铁磁的转变,取而代之的是一种顺磁至反铁磁的转变过程。
第四章和第五章,对样品的红外光学和拉曼光谱进行了研究。对于未掺杂的样品(x=0),高温区域其远红外反射光谱很明显呈现出四个特征峰；但其中两个峰会随着温度的降低逐渐消失。高温下,特征峰的峰位会随温度的降低在铁磁的转变温度处呈现出很大变化。而对于掺杂Y的样品,这四个远红外反射光谱特征峰一直很明显的保持,不会随温度发生变化,尽管在磁性测量研究中表明掺杂Y的样品也会有明显的磁转变行为。但在中红外反射谱中Y掺杂样品在其磁转变温度附近发现很明显的转变。结合Mn06晶格振动模式和Jahn-Teller效应,可以对结果给出了定性解释。每种样品在激光拉曼光谱上都呈现出高波数峰(～610cm-1)、中波数峰(～450cm-1)和低波数峰(-220cm-1)三个明显的特征峰。但其中三个样品峰随温度变化没有较为明显的规律性。
Manganese oxide La1-xCaxMnO3with perovskite structure are paid great attention due to the discovery of colossal magnetoresistive effect inside. The complex interactions among the charge, orbital, spin and lattice give rise to the abundant physics properties, such as metal-insulator transition, magnetic transition, charge-ordering and phase separation. Manganese oxides like La1-yRyRexMnO3(R: rare earth elements Y, Prand Nd ect. with trivalence; Re:alkali elements Ca, Srand Ba ect. with double valence) are deduced from a matrix compound LaMnO3by doping on La sites, resulting in Mn ions with different valences, and consequently changing the crystal structure, electronic and magnetic properties of the matrix, and even intrinsic inhomogeneity at microscale. The inhomogeneity at microscale will inevitably induce the inhomogeneity of dielectric constant and magnetic susceptibility, which can be sensed by its far-infrared spectra. The spectra are sensitive to the vibration modes that are closely related to the electron-photo interaction, electron transition between interbands or intrabands and magnetic transitions.
The Y-doped manganese oxides La2/3-xYxCa1/3Mn03(x=0,0.07,0.1, and0.14) were sintered by a solid-state method. Their crystal structures, magnetic and electronic transport properties, reflectivity of mid/far infrared radiation spectra, and laser confocal microscopic Raman spectra were checked and characterized. The whole thesis is arranged as follow.
In chapter one, a brief introduction on the crystal structures, electro-magnetic properties, characterization methods of manganites and the aim of the thesis was expressed.
In chapter two, much attention was paid to the preparation of La2/3-xYxCai/3Mno3(X=0,0.07,0.1, and0.14) and the experimental setup of infrared and laser confocal microscopic Raman spectra analysis.
In chapter three, a X-ray diffractionmeter was employed to analyze structure of=0,0.07,0.1, and0.14). The resistivity of the samples were detected by a four-probe method from75K-300K; for lower doping-level samples, is was found a metallic state at low temperature and insulator-like conducting state at high temperature. And the transition temperature moves towards lower temperature with Y doping and the transition even disappears at x=0.14, in which the sample only shows an insulating behavior. The diffraction peaks move to the high angle for the four samples with Y increasing. The magnetic properties of these manganese La2/3-xYxCa1/3MnO3(x=0,0.07,0.1, and0.14) were checked with a SQUID under H=10Oe. It was found that ferromagnetic transition temperature (i.e. the Curie temperature Tc) decrease significantly with incensement of Y doping. When the doping level x=0.14, the sample does not show the paramagnetic to ferromagnetic transition, replaced by a paramagnetic to antiferromagnetic transition instead.
In chapter five, the infrared optical properties and Raman spectra of the samples were shown. For the undoped sample, four characteristic peaks in the far infrared radiation spectrum can be found at high temperatures and with the decrease of temperature two of them gradually fade away. The peak positions show a great change around the magnetic transition temperature of the sample. For the Y-doped samples, the four peaks become clearer. Although their magnetic properties also show sharp changes, the shape of the four peaks is stable and almost independent of temperature. However, there is a manifest change in the mid infrared radiation spectrum around the magnetic transitions. A qualitative explanation was proposed for the above results by taking the lattice vibration modes of Jahn-Teller effect in the Mn-o octahedral lattice into consideration. Three obvious characteristic peaks, high wave number peaks (～610cm-1), medium wave number peaks (～450cm-1) and low wave number peaks (～220cm-1), appear in Raman spectrum for each sample.But the other three peaks show no obvious changes with temperature.
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