ZnO薄膜及其发光器件的PLD法制备研究
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摘要
ZnO是一种宽禁带半导体材料,为六方晶体(纤锌矿)结构,与GaN的晶格结构相同。室温下ZnO的禁带宽度为3.37eV左右,激子束缚能为60meV,是继GaN之后的又一理想的光电材料。
激光脉冲沉积(PLD)法是近年来发展起来的先进的薄膜生长技术,它是在高真空背景下用高能激光烧蚀ZnO靶材生成蒸发物淀积在加热衬底上生长晶体薄膜的。本论文利用PLD技术在半绝缘(001)取向的GaAs单晶片上制备ZnO薄膜,在400℃退火条件下,通过As扩散成功制备了P型ZnO薄膜。继而按照p型ZnO薄膜的制备条件,成功制备了p-ZnO/n+-GaAs异质结发光器件。在室温下电致发光测试中,即可以测试到ZnO层缺陷深能级的蓝绿电致发光谱,同时也测试到GaAs层的红外电致发光谱。在此基础上,对ZnO同质p-n结发光器件的制备进行了初步研究。
ZnO is a wide direct band gap semiconductor with band gap of 3.37eV and exciton binding energy of 60 meV at room temperature. It has the same structure as GaN and become a new opto-electronic material for application in new optical devices as a promising substrate material for GaN.
Pulsed laser deposition(PLD)is a newly developed film growth technique. In this technique, high density laser ablates the target and produces ZnO plume depositing on heated substrate in high vacuum background. In this thesis, we use the PLD technology in the semi-insulating (001)-oriented single-chip GaAs prepared ZnO thin film. in the annealing 400℃conditions, the successful adoption of preparation As the spread of the P-film Zn0. then In accordance with our p-type ZnO thin films prepared by the conditions,We have successfully prepared p-ZnO / n +-GaAs heterojunction devices.At room temperature electroluminescence test, which can be tested to the deep level defects ZnO layer of electric blue-green spectrum, but also to test GaAs layer of electric infrared spectra.On this basis,we have preliminary studied Zn0 homogeneous pn junction light-emitting devices preparation.
激光脉冲沉积(PLD)法是近年来发展起来的先进的薄膜生长技术,它是在高真空背景下用高能激光烧蚀ZnO靶材生成蒸发物淀积在加热衬底上生长晶体薄膜的。本论文利用PLD技术在半绝缘(001)取向的GaAs单晶片上制备ZnO薄膜,在400℃退火条件下,通过As扩散成功制备了P型ZnO薄膜。继而按照p型ZnO薄膜的制备条件,成功制备了p-ZnO/n+-GaAs异质结发光器件。在室温下电致发光测试中,即可以测试到ZnO层缺陷深能级的蓝绿电致发光谱,同时也测试到GaAs层的红外电致发光谱。在此基础上,对ZnO同质p-n结发光器件的制备进行了初步研究。
ZnO is a wide direct band gap semiconductor with band gap of 3.37eV and exciton binding energy of 60 meV at room temperature. It has the same structure as GaN and become a new opto-electronic material for application in new optical devices as a promising substrate material for GaN.
Pulsed laser deposition(PLD)is a newly developed film growth technique. In this technique, high density laser ablates the target and produces ZnO plume depositing on heated substrate in high vacuum background. In this thesis, we use the PLD technology in the semi-insulating (001)-oriented single-chip GaAs prepared ZnO thin film. in the annealing 400℃conditions, the successful adoption of preparation As the spread of the P-film Zn0. then In accordance with our p-type ZnO thin films prepared by the conditions,We have successfully prepared p-ZnO / n +-GaAs heterojunction devices.At room temperature electroluminescence test, which can be tested to the deep level defects ZnO layer of electric blue-green spectrum, but also to test GaAs layer of electric infrared spectra.On this basis,we have preliminary studied Zn0 homogeneous pn junction light-emitting devices preparation.
引文
[1]徐毓龙.氧化物与化合物半导体基础[M].陕西:西安电子科技大学出版社1991:18
[2] Suchea M, Christoulakis S, Katsarakis N, et al. Comparative study of zinc oxide and aluminum doped zinc oxide transparent thin films grown by direct current magnetron sputtering[J]. Thin Solid Films, 515{16): 65626566
[3] Rozati S M, Akesteh Sh. Characterization of ZnO: Al thin films obtained by spray pyrolysis technique[J]. Materials Characterization, 58{4): 319-322
[4] Lee J, Lee D, Lim D, -et al. Structural, electrical and optical properties of ZnO:Al films deposited on tlexibie organic substrates for solar cell applications[J].Thin Solid Films, 2007, 515(I5): 60946098
[5] Rican S, Caglar Y, Caglar M, et al. Electrical conductivity, optical and structural properties of indium-doped ZnO nanofiber thin film deposited by spray pyrolysis method[J]. Physica E: Low-dimensional Systems and Nanostructures, 35{1): 131-138
[6] Lucio-Lopez M A, Maldonado A, Castanedo-Perez R, et al. Thickness dependence of ZnO: In thin films doped with different indium compounds and deposited by chemical spray[J]. Sol. Energy Mater. Sol. Cells, 2006, 90{15):2362-2376
[7] Lima S A M, Davolos M R, Legnani C, et al. Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films[J]. Journal of Alloys and Compounds, 418(1-2):3538
[8] Jin C M, Narayan R, Tiwari A, et al. Epitaxial growth of zinc oxide thin films on silicon[J]. Materials Science and Engineering B, 2005, 117(3): 348-354
[9] Zu P, Tang Z K, Wong G K L, et al. Ultraviolet spontaneous and stimulated emissions from ZnO microcrystallite thin films at room temperature[J]. SolidState Commun, 1997, 103(8): 459-463
[10]王卿璞,张德恒,马洪磊,等.射频磁控溅射法制备ZnO薄膜的绿光发射[J].发光学报,2004, 25(3): 291-294
[11]李伙全,宁兆元,程珊华,等.射频磁控溅射沉积的ZnO薄膜的光致发光中心与漂移[J].物理学报,2004, 53(3): 867-870
[12] Bagnall D M, Chen Y F, Shen M Y, et al. Room temperature excitonic stimulated emission from zinc oxide epilayers grown by plasma-assisted MBE[J]. J. Cryst. Growth, 1998, 184/185: 605-609
[13] Kim H, Horw Itz J S, Kim W H, et al. Chrisey doped ZnO thin films as a node materials for organic.light emitting diodes[J]. Thin Solid Films, 2002, 420-421:539-543
[14] Zhang D H, Brodie D E. Crystallite orientation and the related photoresponse of hexagonal ZnO films deposited by r.f. sputtering[J]. Thin Solid Films, 1994, 251(2): 151-156
[15] Zhang D H, Brodie D E. Photoresponse of polycrystalline ZnO films deposited by r.f. bias sputtering[J]. ThimSolid Films, 1995, 261(1-2): 334-339
[16]邓宏,徐自强,谢娟,等.ZnO基紫外探测器研究进展[[J].物理,2006, 35(7):595-598 [17」张德恒.用射频偏压溅射制备的具有快速紫外光响应的ZnO薄膜半导体学报,1995,16(10): 79-782
[18] Zhuxi Fu, Bixia Lin, Guihong Liao, Ziqin Wu. The effect of Zn buffer layer on growth and luminescence of ZnO films deposited on Si substrates Journal of Crystal Growth.1998,193(3):16-320
[19]邹璐,叶志镇,黄靖云,赵炳辉.脉冲激光沉积法生长Znl-xMgxO薄膜.半导体学报,2002, 23(12): 1291-1294
[20]郭宝增,王永青,宗晓萍,孙荣霞,宋登元.ZnO材料的电子输运特性.半导体学报,2003, 23(7): 723-728
[21]马勇,王万录,廖克俊,吕建伟,孙晓楠.ZnO薄膜的光致发光.功能材料,2004, 35(2):139-144
[22]徐伟中,叶志镇,周婷,赵炳辉,朱丽萍,黄靖云.MOCVD法以NO气体为掺杂源生长p型ZnO薄膜.半导体学报,2005, 26(1): 38-41
[23]温战华.王立.方文卿.蒲勇.罗小平.郑畅达.戴江南.江风益.退火温度对ZnO薄膜结构和发光性能的影响半导体学报,2005, 26(1): 498-SO1
[24] Toshiyuki Nakamura, Hideki Minoura, Hachizio Muto. Fabrication of ZnO(0001) epitaxial films on the cubic(111) substrate with C6 symmetry by pulsed laser ablation. Thin Solid Films 2002, 405(1-2):109-116
[25]Wang Zhao-yang, Hu Li-thong, Zhao Jie, Sun Jie, Wang Zhi-jun. Effect of the variation of temperature on the structural and optical properties of ZnO thin filins prepared on Si (1 1 1) substrates using PLD. Vacuum, 2005, 78(1) 53-57
[26] Sang Sub Kim, Byung-Teak Lee. Effects of oxygen pressure on the growth of pulsed laser deposited ZnO films on Si(001). Thin Solid Films, 2004, 446 (2): 307-312
[27]徐彭寿,徐彭寿.孙玉明.施朝淑.徐法强.潘海斌.施朝淑.ZnO及其缺陷电子结构对光谱特性的影响.红外与毫米波学报,2002, 21(S1): 91-96
[28] Xu peng-shoo, Sun Yu-ming, Shi Chao-shu. Electronic structureof ZnO and it's defects.Science in China (A), 2001, 44(9): 1174-1181
[29] JQP. Wang, D.H. Zhang, Z.Y. Xue, X. T. Hao. Violet luminescence emitted from ZnO films deposited on Si substrate by rf magnetron sputtering.却plied Surface Science, 2002,201(1-4):123-128
[30] Payne M C, Teter M P, Ahan D C,et al. Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugategradients Rev. Mod. Phys., 1992,64: 1045-1097
[31]李承斌.过渡金属及其碳、氮化物力学性质的第一性原理研究.〔博士学位论文〕,武汉:武汉大学,2005
[32] P.Wang, NuoFu Chen, Z.G.Yin. P-doped p-type ZnO films deposited on Si substrate by radio-frequence magnetron sputtering. Appl.Phys.Lett, 2006, 88(15): 21021-21023
[33] T Yamamoto, H.Katayama-Yoshida. Unipolarity of ZnO with a wide-band gap and its solution using codoping method. J.Crystal Growth, 2000,214/215:552-555
[34] D. P. Norton, Y. W. Heo, M. P. Lvill, K. Ip, S. J. Pearton, ZnO: growth,doping and processing, Materials Today, 2004, 3: 34.
[35]王丽玉,谢家纯,林碧霞,王克彦,傅竹西.n-ZnO/p-Si异质结UV增强型光电探测器的研究.电子元件与材料,2004, 23(01): 42.
[36]刘益春,陈艳伟,申德振.ZnO一维纳米线及其异质结构的外延生长.物理,2005, 34 (9):654.
[37]叶志镇,张银珠,陈汉鸿,何乐年.ZnO光电导紫外探测器的制备和特性研究.电子学报,2003,31(11): 1605.
[38] Y. Liu, R. C. Gorla, S. Liang, Ultraviolet detectors based on epitaxial ZnO film grown by MOCVD, J.Elec. Mater., 2000, 29(1): 60.
[39] Wei Yang, Wide bandgap MgXZn_XO semiconducting thin film and applications to solar visible blindultraviolet photodetectors, Dissertation of University of Maryland, USA, 2002.
[40]陈光华.新型电子薄膜材料.化学工业出版社,2002.
[41]李美成,陈学康,杨建平等.脉冲激光纳米薄膜制备技术.红外与激光工程,2000, 29(6): 31-35.
[42]叶志镇,张银珠,徐伟中,ZnO薄膜P型掺杂的研究进展,无机材料学报,2003,18:11-18.
[43]杨秀健,施朝淑,许小亮,ZnO薄膜P型掺杂的研究进展,无机材料学报,2003,18:-10.
[44] J.M. Bian, X.M. Li, X.D. Gao, et al., Deposition and electrical properties of N-In codoped p-type ZnO films by ultrasonic spary pyrolysis. Appl. Phys. Lett. 2004, 84(4): p541.
[45] J.M. Bian, X.M. Li, C.Y. Zhang, et al., Synthesis and characterization of two-layer-structured ZnO p-n homojunctions by ultrasonic spray pyrolysis. Appl. Phys. Lett. 2004, 84(19): p3783.
[46] Wang Z Y, Hu L Z, Zhao J, et al. Effect of the variation of temperature on the structural and optical properties of ZnO thin films prep substrates using PLD[J]. Vacuum, 2005, 78(1): 5357 on Si (1 l 1).
[2] Suchea M, Christoulakis S, Katsarakis N, et al. Comparative study of zinc oxide and aluminum doped zinc oxide transparent thin films grown by direct current magnetron sputtering[J]. Thin Solid Films, 515{16): 65626566
[3] Rozati S M, Akesteh Sh. Characterization of ZnO: Al thin films obtained by spray pyrolysis technique[J]. Materials Characterization, 58{4): 319-322
[4] Lee J, Lee D, Lim D, -et al. Structural, electrical and optical properties of ZnO:Al films deposited on tlexibie organic substrates for solar cell applications[J].Thin Solid Films, 2007, 515(I5): 60946098
[5] Rican S, Caglar Y, Caglar M, et al. Electrical conductivity, optical and structural properties of indium-doped ZnO nanofiber thin film deposited by spray pyrolysis method[J]. Physica E: Low-dimensional Systems and Nanostructures, 35{1): 131-138
[6] Lucio-Lopez M A, Maldonado A, Castanedo-Perez R, et al. Thickness dependence of ZnO: In thin films doped with different indium compounds and deposited by chemical spray[J]. Sol. Energy Mater. Sol. Cells, 2006, 90{15):2362-2376
[7] Lima S A M, Davolos M R, Legnani C, et al. Low voltage electroluminescence of terbium- and thulium-doped zinc oxide films[J]. Journal of Alloys and Compounds, 418(1-2):3538
[8] Jin C M, Narayan R, Tiwari A, et al. Epitaxial growth of zinc oxide thin films on silicon[J]. Materials Science and Engineering B, 2005, 117(3): 348-354
[9] Zu P, Tang Z K, Wong G K L, et al. Ultraviolet spontaneous and stimulated emissions from ZnO microcrystallite thin films at room temperature[J]. SolidState Commun, 1997, 103(8): 459-463
[10]王卿璞,张德恒,马洪磊,等.射频磁控溅射法制备ZnO薄膜的绿光发射[J].发光学报,2004, 25(3): 291-294
[11]李伙全,宁兆元,程珊华,等.射频磁控溅射沉积的ZnO薄膜的光致发光中心与漂移[J].物理学报,2004, 53(3): 867-870
[12] Bagnall D M, Chen Y F, Shen M Y, et al. Room temperature excitonic stimulated emission from zinc oxide epilayers grown by plasma-assisted MBE[J]. J. Cryst. Growth, 1998, 184/185: 605-609
[13] Kim H, Horw Itz J S, Kim W H, et al. Chrisey doped ZnO thin films as a node materials for organic.light emitting diodes[J]. Thin Solid Films, 2002, 420-421:539-543
[14] Zhang D H, Brodie D E. Crystallite orientation and the related photoresponse of hexagonal ZnO films deposited by r.f. sputtering[J]. Thin Solid Films, 1994, 251(2): 151-156
[15] Zhang D H, Brodie D E. Photoresponse of polycrystalline ZnO films deposited by r.f. bias sputtering[J]. ThimSolid Films, 1995, 261(1-2): 334-339
[16]邓宏,徐自强,谢娟,等.ZnO基紫外探测器研究进展[[J].物理,2006, 35(7):595-598 [17」张德恒.用射频偏压溅射制备的具有快速紫外光响应的ZnO薄膜半导体学报,1995,16(10): 79-782
[18] Zhuxi Fu, Bixia Lin, Guihong Liao, Ziqin Wu. The effect of Zn buffer layer on growth and luminescence of ZnO films deposited on Si substrates Journal of Crystal Growth.1998,193(3):16-320
[19]邹璐,叶志镇,黄靖云,赵炳辉.脉冲激光沉积法生长Znl-xMgxO薄膜.半导体学报,2002, 23(12): 1291-1294
[20]郭宝增,王永青,宗晓萍,孙荣霞,宋登元.ZnO材料的电子输运特性.半导体学报,2003, 23(7): 723-728
[21]马勇,王万录,廖克俊,吕建伟,孙晓楠.ZnO薄膜的光致发光.功能材料,2004, 35(2):139-144
[22]徐伟中,叶志镇,周婷,赵炳辉,朱丽萍,黄靖云.MOCVD法以NO气体为掺杂源生长p型ZnO薄膜.半导体学报,2005, 26(1): 38-41
[23]温战华.王立.方文卿.蒲勇.罗小平.郑畅达.戴江南.江风益.退火温度对ZnO薄膜结构和发光性能的影响半导体学报,2005, 26(1): 498-SO1
[24] Toshiyuki Nakamura, Hideki Minoura, Hachizio Muto. Fabrication of ZnO(0001) epitaxial films on the cubic(111) substrate with C6 symmetry by pulsed laser ablation. Thin Solid Films 2002, 405(1-2):109-116
[25]Wang Zhao-yang, Hu Li-thong, Zhao Jie, Sun Jie, Wang Zhi-jun. Effect of the variation of temperature on the structural and optical properties of ZnO thin filins prepared on Si (1 1 1) substrates using PLD. Vacuum, 2005, 78(1) 53-57
[26] Sang Sub Kim, Byung-Teak Lee. Effects of oxygen pressure on the growth of pulsed laser deposited ZnO films on Si(001). Thin Solid Films, 2004, 446 (2): 307-312
[27]徐彭寿,徐彭寿.孙玉明.施朝淑.徐法强.潘海斌.施朝淑.ZnO及其缺陷电子结构对光谱特性的影响.红外与毫米波学报,2002, 21(S1): 91-96
[28] Xu peng-shoo, Sun Yu-ming, Shi Chao-shu. Electronic structureof ZnO and it's defects.Science in China (A), 2001, 44(9): 1174-1181
[29] JQP. Wang, D.H. Zhang, Z.Y. Xue, X. T. Hao. Violet luminescence emitted from ZnO films deposited on Si substrate by rf magnetron sputtering.却plied Surface Science, 2002,201(1-4):123-128
[30] Payne M C, Teter M P, Ahan D C,et al. Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugategradients Rev. Mod. Phys., 1992,64: 1045-1097
[31]李承斌.过渡金属及其碳、氮化物力学性质的第一性原理研究.〔博士学位论文〕,武汉:武汉大学,2005
[32] P.Wang, NuoFu Chen, Z.G.Yin. P-doped p-type ZnO films deposited on Si substrate by radio-frequence magnetron sputtering. Appl.Phys.Lett, 2006, 88(15): 21021-21023
[33] T Yamamoto, H.Katayama-Yoshida. Unipolarity of ZnO with a wide-band gap and its solution using codoping method. J.Crystal Growth, 2000,214/215:552-555
[34] D. P. Norton, Y. W. Heo, M. P. Lvill, K. Ip, S. J. Pearton, ZnO: growth,doping and processing, Materials Today, 2004, 3: 34.
[35]王丽玉,谢家纯,林碧霞,王克彦,傅竹西.n-ZnO/p-Si异质结UV增强型光电探测器的研究.电子元件与材料,2004, 23(01): 42.
[36]刘益春,陈艳伟,申德振.ZnO一维纳米线及其异质结构的外延生长.物理,2005, 34 (9):654.
[37]叶志镇,张银珠,陈汉鸿,何乐年.ZnO光电导紫外探测器的制备和特性研究.电子学报,2003,31(11): 1605.
[38] Y. Liu, R. C. Gorla, S. Liang, Ultraviolet detectors based on epitaxial ZnO film grown by MOCVD, J.Elec. Mater., 2000, 29(1): 60.
[39] Wei Yang, Wide bandgap MgXZn_XO semiconducting thin film and applications to solar visible blindultraviolet photodetectors, Dissertation of University of Maryland, USA, 2002.
[40]陈光华.新型电子薄膜材料.化学工业出版社,2002.
[41]李美成,陈学康,杨建平等.脉冲激光纳米薄膜制备技术.红外与激光工程,2000, 29(6): 31-35.
[42]叶志镇,张银珠,徐伟中,ZnO薄膜P型掺杂的研究进展,无机材料学报,2003,18:11-18.
[43]杨秀健,施朝淑,许小亮,ZnO薄膜P型掺杂的研究进展,无机材料学报,2003,18:-10.
[44] J.M. Bian, X.M. Li, X.D. Gao, et al., Deposition and electrical properties of N-In codoped p-type ZnO films by ultrasonic spary pyrolysis. Appl. Phys. Lett. 2004, 84(4): p541.
[45] J.M. Bian, X.M. Li, C.Y. Zhang, et al., Synthesis and characterization of two-layer-structured ZnO p-n homojunctions by ultrasonic spray pyrolysis. Appl. Phys. Lett. 2004, 84(19): p3783.
[46] Wang Z Y, Hu L Z, Zhao J, et al. Effect of the variation of temperature on the structural and optical properties of ZnO thin films prep substrates using PLD[J]. Vacuum, 2005, 78(1): 5357 on Si (1 l 1).