【摘要】：ZnO及其它Ⅱ-Ⅵ族半導(dǎo)體材料由于其優(yōu)異的性能而在光電、壓電、熱電、鐵電等諸多領(lǐng)域被廣泛應(yīng)用。自上世紀(jì)90年代ZnO薄膜在室溫下發(fā)生光泵浦激發(fā)近紫外激光發(fā)射的現(xiàn)象被報(bào)道后,ZnO作為新型的光電信息功能材料引起了研究熱潮。然而要實(shí)現(xiàn)ZnO在光電器件上的應(yīng)用,必須解決ZnO的能帶工程(能隙調(diào)控)和p型摻雜兩大關(guān)鍵問題。ZnO的能帶調(diào)控一般通過等價(jià)離子的取代來實(shí)現(xiàn),例如陽離子部分取代Zn形成MeZnO(Me = Mg,Be,Cd等)三元合金或陰離子取代O形成ZnOX(X = S,Se,Te等)三元合金。研究表明,等價(jià)陽離子部分取代Zn形成的MeZnO(Me = Be,Mg,Cd等)合金中會存在相分離,并且Me的固溶度有限。在理論上,目前對Ⅱ-Ⅵ族三元合金的固溶體性質(zhì)進(jìn)行深入研究的報(bào)道比較少。本文采用第一性原理計(jì)算結(jié)合集團(tuán)展開法,研究了CdxZn1-xO、BexZn1-xO、MgxZn1-xO、CdO1-xSx和ZnS1-xSe等Ⅱ-Ⅵ族三元合金固溶體的熱力學(xué)性質(zhì)。分析了不同成分下 CdxZn1-xO、BexZn1-xO、MgxZn1-xO、CdO1-xSx和ZnS1-xSex等三元合金的形成能和相圖,主要研究內(nèi)容及結(jié)論如下:(1)計(jì)算了纖鋅礦(WZ)和巖鹽礦(RS)CdxZn1-xO三元合金的形成能和相圖。通過形成能的計(jì)算,發(fā)現(xiàn)大部分CdxZn1-xO合金構(gòu)型的形成能都大于零,表明ZnO和CdO在低溫下難于結(jié)合形成固溶體。進(jìn)一步計(jì)算發(fā)現(xiàn)了 WZ-CdxZn1-xO合金的兩個(gè)亞穩(wěn)相結(jié)構(gòu)(Cd1/3Zn2/3O 和 Cd2/3Zn1/3O)。對 Cd1/3Zn2/3O 和 Cd2/3Zn1/3O 兩個(gè)亞穩(wěn)相的晶格常數(shù)a和c、鍵長、O-Zn(Cd)-O鍵角以及電子結(jié)構(gòu)進(jìn)行分析發(fā)現(xiàn),隨著Cd在WZ-CdxZn1-xO合金中含量的增大,晶格常數(shù)a和c都逐漸增大,然而晶格常數(shù)的比值c/a逐漸減小。同樣,隨著Cd摻雜量的增大,O-Zn(Cd)-O鍵角大小和能帶帶隙逐漸變小。計(jì)算分析了纖鋅礦和巖鹽礦結(jié)構(gòu)CdxZn1-xO的有效集團(tuán)交互系數(shù),發(fā)現(xiàn)雙原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo),表明雙原子組成的集團(tuán)對形成能的貢獻(xiàn)最大。通過計(jì)算WZ-CdxZn1-xO和RS-CdxZn1xO合金的兩相相圖,發(fā)現(xiàn)在1600 K時(shí)Cd在WZ-ZnO中的固溶度為0.13,然而Zn在RS-CdO中的固溶度為0.01。(2)計(jì)算了纖鋅礦和閃鋅礦結(jié)構(gòu)(ZB)BexZn1-xO的形成能和熱力學(xué)相圖。通過形成能的計(jì)算,發(fā)現(xiàn)大部分BexZn1-xO合金構(gòu)型的形成能都大于零,表明ZnO與BeO在低溫下難于結(jié)合形成固溶體。WZ-BexZn1-xO和ZB-BexZn1-x)的有效集團(tuán)交互系數(shù)計(jì)算顯示,對于WZ-BexZn1-xO來說,雙原子和四個(gè)原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo)作用,表明雙原子和四個(gè)原子的集團(tuán)對形成能的貢獻(xiàn)最大。對于ZB-BexZn1-xO來說,雙原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo),表明雙原子組成的集團(tuán)對形成能的貢獻(xiàn)最大。文章通過計(jì)算纖鋅礦和閃鋅礦BexZn1-xO的相圖發(fā)現(xiàn),聲子振動對纖鋅礦和閃鋅礦BexZn1xO的相圖影響很大。晶格振動對Be(Zn)在ZnO(BeO)中的固溶度具有很大的影響。(3)計(jì)算了纖鋅礦和巖鹽礦結(jié)構(gòu)MgxZn1-xO合金的形成能和熱力學(xué)相圖。通過計(jì)算MgxZn1-xO的形成能,發(fā)現(xiàn)在低溫下大部分MgxZn1-xO合金構(gòu)型的形成能都小于零,表明ZnO與MgO在低溫下容易結(jié)合形成固溶體。同樣計(jì)算了纖鋅礦和巖鹽礦結(jié)構(gòu)MgxZn1-xO的有效集團(tuán)交互系數(shù)。由有效集團(tuán)交互系數(shù)得出對MgxZn1-xO來說,雙原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo),表明雙原子組成的集團(tuán)對MgxZn1-xO形成能的貢獻(xiàn)最大。對WZ-MgxZn1-xO和RS-MgxZn1-xO的兩相相圖分析發(fā)現(xiàn)Mg較難固溶于纖鋅礦型的ZnO中,而Zn較容易固溶于巖鹽礦結(jié)構(gòu)的MgO中。(4)計(jì)算了纖鋅礦和巖鹽礦結(jié)構(gòu)CdO1-xSx的形成能和熱力學(xué)相圖。通過計(jì)算CdO1-xSx的形成能,發(fā)現(xiàn)大部分CdO1-xSx合金構(gòu)型的形成能都大于零,表明在低溫下CdO與CdS難于結(jié)合形成固溶體。同樣計(jì)算了纖鋅礦和巖鹽礦結(jié)構(gòu)CdO1-xSx的有效集團(tuán)交互系數(shù)。雙原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo),表明雙原子組成的集團(tuán)對CdO1-xSx形成能的貢獻(xiàn)最大。計(jì)算和分析了 WZ-CdO1-xSx和RS-CdO1-xSx的兩相相圖,研究得到S較難固溶于RS-CdO中,而O較容易固溶于WZ-CdS中。(5)對WZ-ZnS1-xSex和ZB-ZnS1-xSex的形成能和相圖等熱力學(xué)性質(zhì)進(jìn)行了研究。通過計(jì)算纖鋅礦和閃鋅礦結(jié)構(gòu)ZnS1-xSex的形成能,發(fā)現(xiàn)大部分ZnS1-xSex合金構(gòu)型的形成能都大于零,表明ZnS與ZnSe在低溫下難于結(jié)合形成固溶體。由有效集團(tuán)交互系數(shù)分析發(fā)現(xiàn)雙原子組成的集團(tuán)在有效集團(tuán)交互系數(shù)中占主導(dǎo),表明雙原子組成的集團(tuán)對形成能的貢獻(xiàn)最大。計(jì)算并且分析了 ZnS1-xSex合金的x-T相圖,發(fā)現(xiàn)不管是纖鋅礦結(jié)構(gòu)還是閃鋅礦結(jié)構(gòu)合金,Se在ZnS中的固溶度與S在ZnSe中的固溶度基本上相等。對于上述5個(gè)體系的半導(dǎo)體合金,通過比較發(fā)現(xiàn)集團(tuán)展開法計(jì)算的形成能和采用第一性原理計(jì)算的形成能兩者基本相等,從而證實(shí)了采用集團(tuán)展開法計(jì)算合金形成能的有效性與可行性。
[Abstract]:ZnO and other II-VI semiconductor materials are widely used in the fields of photoelectric, piezoelectric, pyroelectric, ferroelectric and the like due to its excellent performance. As the phenomenon of ZnO thin film excited near-ultraviolet laser emission at room temperature has been reported in the 1990s, ZnO as a new type of photoelectric information function material has caused a research upsurge. However, it is necessary to solve the two key problems of the energy band engineering (energy gap regulation) and p-type doping of ZnO. The energy band regulation of ZnO is generally realized by the substitution of equivalent ions, for example, the cation part is substituted for Zn to form a ternary alloy of MeZnO (Me = Mg, Be, Cd, etc.) or an anion-substituted O to form a ternary alloy of ZnOX (X = S, Se, Te, etc.). The results show that the equivalent cation part is substituted for Zn-formed MeZnO (Me = Be, Mg, Cd, etc.), and the solid solubility of Me is limited. In theory, there are few reports on the solid solution properties of the II-VI ternary alloy. In this paper, the thermodynamic properties of CdxZn1-xO, BxZn1-xO, MgxZn1-xO, CdO1-xSx and ZnS1-xSe and other II-VI ternary alloy solid solutions are studied by the first principle calculation and the group expansion method. The formation energy and phase diagram of CdxZn1-xO, BxZn1-xO, MgxZn1-xO, CdO1-xSx and ZnS1-xSx are analyzed. The main contents and conclusions are as follows: (1) The formation energy and phase diagram of wurtzite (WZ) and rock salt (RS) CdxZn1-xO ternary alloy are calculated. The formation energy of most of the CdxZn1-xO alloy configurations was found to be greater than zero by the formation of energy, indicating that ZnO and CdO were difficult to combine to form a solid solution at low temperatures. Two metastable phase structures of the WZ-CdxZn1-xO alloy (Cd1/ 3Zn2/ 3O and Cd2/ 3Zn1/ 3O) were further calculated. The lattice constants a and c, the bond length, the O-Zn (Cd)-O bond angle and the electronic structure of the two metastable phases of Cd1/ 3Zn2/ 3O and Cd2/ 3Zn1/ 3O are found, and the lattice constants a and c are gradually increased with the increase of the content of Cd in the WZ-CdxZn1-xO alloy, but the ratio c/ a of the lattice constant is gradually reduced. Similarly, with the increase of Cd doping, the size of the O-Zn (Cd)-O bond and the band gap are gradually reduced. The effective group interaction coefficient of wurtzite and the structure of CdxZn1-xO is calculated and analyzed, and the group of two atoms is found to be dominant in the effective group interaction coefficient, indicating that the two-atom group has the greatest contribution to the formation energy. By calculating the two-phase phase diagram of the WZ-CdxZn1-xO and RS-CdxZn1xO alloys, the solid solubility of Cd in WZ-ZnO at 1600 K was 0.13, but the solid solubility of Zn in the RS-CdO was 0.01. (2) The formation energy and the thermodynamic phase diagram of wurtzite and sphalerite structure (ZB) BexZn1-xO were calculated. The formation energy of most of the BexZn1-xO alloy configurations was found to be greater than zero by the formation of energy, indicating that ZnO and BeO were difficult to combine at low temperature to form a solid solution. The effective group interaction coefficient calculation of WZ-BexZn1-xO and ZB-BexZn1-x shows that, for the WZ-BexZn1-xO, the group of the two atoms and the four atoms take the leading role in the effective group interaction coefficient, indicating that the group of the two atoms and the four atoms has the greatest contribution to the formation energy. For ZB-BexZn1-xO, the two-atom group is dominant in the effective group interaction coefficient, indicating that the two-atom group has the greatest contribution to the formation energy. The phase diagram of wurtzite and sphalerite BexZn1-xO shows that the phase diagram of wurtzite and sphalerite BexZn1xO has a great effect on the phase diagram of wurtzite and sphalerite. The lattice vibration has a great influence on the solid solubility of Be (Zn) in ZnO (BeO). (3) The formation energy and the thermodynamic phase diagram of the MgxZn1-xO alloy of wurtzite and rock salt are calculated. By calculating the formation energy of MgxZn1-xO, it is found that the formation energy of most of the MgxZn1-xO alloy configuration at low temperature can be less than zero, indicating that ZnO and MgO are easy to bond to form a solid solution at low temperature. The effective group interaction coefficients of wurtzite and halite structural MgxZn1-xO were also calculated. For MgxZn1-xO by the effective group interaction coefficient, the group of two atoms is dominant in the effective group interaction coefficient, indicating that the two-atom group has the greatest contribution to the formation of the MgxZn1-xO. The two-phase phase diagram of WZ-MgxZn1-xO and RS-MgxZn1-xO has found that Mg is hard to be dissolved in the wurtzite type ZnO, and the Zn is more easily soluble in the MgO of the rock salt ore structure. (4) The formation energy and the thermodynamic phase diagram of wurtzite and halite structure CdO1-xSx are calculated. By calculating the formation energy of CdO1-xSx, the formation energy of most of the CdO1-xSx alloy configurations is found to be greater than zero, indicating that CdO and CdS are difficult to combine to form a solid solution at low temperatures. The effective group interaction coefficients of wurtzite and halite structures, CdO1-xSx, are also calculated. The two-atom group is dominant in the effective group interaction coefficient, indicating that the two-atom group has the greatest contribution to the formation of the CdO1-xSx. The two-phase phase diagram of WZ-CdO1-xSx and RS-CdO1-xSx was calculated and analyzed. (5) The thermodynamic properties of the formation energy and phase diagram of WZ-ZnS1-xSx and ZB-ZnS1-xSx are studied. By calculating the formation energy of ZnS1-xSx of wurtzite and sphalerite structure, the formation energy of most of the ZnS1-xSx alloy configurations is found to be greater than zero, indicating that ZnS and ZnSe are difficult to combine to form a solid solution at low temperature. The analysis of the effective group interaction coefficient shows that the group of two atoms is dominant in the effective group interaction coefficient, indicating that the two-atom group has the greatest contribution to the formation energy. The x-T phase diagram of ZnS1-xSx alloy is calculated and analyzed. It is found that the solid solubility of Se in ZnS is substantially the same as that of S in ZnSe, whether wurtzite structure or sphalerite structure alloy. For the above-mentioned semiconductor alloy of the five systems, the formation energy calculated by the expansion method of the group and the formation energy calculated by the first principle are basically the same, so that the validity and the feasibility of the formation energy of the alloy are calculated by the method of the group expansion.
【學(xué)位授予單位】：湖北大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TN304

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7 周，

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