溶胶—凝胶法制备ZnO薄膜工艺优化及其压敏特性研究
摘要
ZnO是一种Ⅱ-Ⅵ族宽禁带化合物半导体材料，在信息领域有着重要的应用。随着大规模集成电路的不断发展，ZnO薄膜优良的低压压敏特性已经引起研究人员的普遍关注。
本文采用溶胶-凝胶法，在Si(111)衬底上使用旋转涂覆工艺制备了ZnO薄膜。实验应用正交设计的思想，结合XRD测试等方法对制备ZnO薄膜的工艺条件进行了优化，并对压敏特性ZnO薄膜的制备工艺进行了探讨。结果表明：在Si(111)衬底上制备具有高度c轴择优取向性、结晶状况良好的ZnO薄膜的实验方案为：Zn~(2+)浓度为0.35mol／L、陈化温度为50℃、预处理温度为200℃、退火温度为650℃；对于压敏特性ZnO薄膜，掺杂配方为：Bi_2O_3：Sb_2O_3：Co_2O_3：MnO_2：Cr_2O_3：Ni_2O_3=1：2：1：1：1：1、Zn~(2+)：杂质浓度=97 mol％／l：3 mol％／l、退火温度750℃；Al系掺杂浓度范围为0.001-0.01mol／l。
实验测得的ZnO薄膜的非线性系数为8.3～16.12，压敏电压为20V左右，具备良好的压敏特性。
ZnO is a novel II～VI family compound. It is a wide direct-gap semiconductor and has great uses in information age.Following the development of VLSI,ZnO thin films attracts much attention in varistors research field.
In the paper, A Series of ZnO thin films were prepared on Si(111)in the sol-gel process. Applying the theory of orthogonal-design, the technological conditions were optimized after investigation and analysis of the samples by XRD and have a touch to preparing process of ZnO thin films varistors. The results revealed that, for preparing highly oriented along c-axis and films, the optimized growing parameters at Si (111) substrate were: ZnO:0.35mol/l(Zn~(2+))、50℃(agin temperature)、200℃(preheating temperature)、650℃(annealing temperature)and two hours(heating time) ; for ZnO varistors property thin films, the optimized growing parameters were: Bi_2O_3 : Sb_2O_3 : Co_2O_3 : MnO_2 : Cr_2O_3 : Ni_2O_3 = 1: 2: 1: 1: 1: 1 (impurity)、Zn~(2=) : impurity concentration = 97 mol%/l : 3 mol%/l、750℃(annealing temperature) ; AZO: impurity concentration is 0.001-0.1 mol/l.
The result:αof ZnO thin films is 8.3～16.12,U_(1MA) is near 20V.
本文采用溶胶-凝胶法，在Si(111)衬底上使用旋转涂覆工艺制备了ZnO薄膜。实验应用正交设计的思想，结合XRD测试等方法对制备ZnO薄膜的工艺条件进行了优化，并对压敏特性ZnO薄膜的制备工艺进行了探讨。结果表明：在Si(111)衬底上制备具有高度c轴择优取向性、结晶状况良好的ZnO薄膜的实验方案为：Zn~(2+)浓度为0.35mol／L、陈化温度为50℃、预处理温度为200℃、退火温度为650℃；对于压敏特性ZnO薄膜，掺杂配方为：Bi_2O_3：Sb_2O_3：Co_2O_3：MnO_2：Cr_2O_3：Ni_2O_3=1：2：1：1：1：1、Zn~(2+)：杂质浓度=97 mol％／l：3 mol％／l、退火温度750℃；Al系掺杂浓度范围为0.001-0.01mol／l。
实验测得的ZnO薄膜的非线性系数为8.3～16.12，压敏电压为20V左右，具备良好的压敏特性。
ZnO is a novel II～VI family compound. It is a wide direct-gap semiconductor and has great uses in information age.Following the development of VLSI,ZnO thin films attracts much attention in varistors research field.
In the paper, A Series of ZnO thin films were prepared on Si(111)in the sol-gel process. Applying the theory of orthogonal-design, the technological conditions were optimized after investigation and analysis of the samples by XRD and have a touch to preparing process of ZnO thin films varistors. The results revealed that, for preparing highly oriented along c-axis and films, the optimized growing parameters at Si (111) substrate were: ZnO:0.35mol/l(Zn~(2+))、50℃(agin temperature)、200℃(preheating temperature)、650℃(annealing temperature)and two hours(heating time) ; for ZnO varistors property thin films, the optimized growing parameters were: Bi_2O_3 : Sb_2O_3 : Co_2O_3 : MnO_2 : Cr_2O_3 : Ni_2O_3 = 1: 2: 1: 1: 1: 1 (impurity)、Zn~(2=) : impurity concentration = 97 mol%/l : 3 mol%/l、750℃(annealing temperature) ; AZO: impurity concentration is 0.001-0.1 mol/l.
The result:αof ZnO thin films is 8.3～16.12,U_(1MA) is near 20V.
引文
[1]吕建国等．ZnO薄膜应用的最新研究进展．功能材料与器件学报，2002，8(3)：303
[2]傅静，徐政，ZnO压敏电阻器的性能及发展，现代技术陶瓷，2004，1：31
[3]黄炎球等，ZnO薄膜及其性能研究进展，无机材料学报，2001．5：16卷，391～397
[4]纪士东等，氧化锌压敏材料研究与发展进展，陶瓷学报，1997，3，第18卷，第1期：52～55
[5]吕建国，叶志镇．ZnO薄膜的最新研究进展．功能材料，2002，33(6)：581～582
[6]李春明等，纳米ZnO材料的制备与应用研究进展，材料导报，2003，5，第17卷，第5期：39～41
[7]陈艺锋等，湿法合成氧化锌压敏电阻粉体的现状与展望，电子元件与材料，2004，1，第1期：23～26
[8]贾桂林，张海军，谭伟。氧化锌薄膜研究的新进展．材料导报，2003，17：207～209
[9]KING S L，GARDENIERS J G E，BOYD I W．Pulsed laser deposited ZnO for device application[J]．Appl Surf Sci 1996,96-98：811-818
[10]陈志清，谢恒堃。氧化锌压敏瓷及其在电力系统中的应用。水利电力出版社
[11]Suzoki Y, Ohki A, Mizutani T, et al.J.Phys. D:Appl.Phys,1987,20:511-517
[12]Horio N, Hiramatsu M, Nawata M, et al.Vacuum,1998,51(4):719-722
[13]贾锐，曲凡钦，武光明等。功能材料，1999，30(6)：636-638
[14]黄焱球，刘梅冬，等。ZnO陶瓷薄膜的制备及其低压压敏特性[J]。压电与声光，2001，23(5)：384-386
[15]King S L，Gardeniers J G E，Boyd I W Pulsed laser deposited ZnO for devices application[J]．Appl Surf Sci，1996,96-98：811
[16]杨邦朝．薄膜物理与技术．高等学校教材
[17]周英．溶胶-凝胶法制备ZnO薄膜．电子科技大学．硕士学位论文．2005-1-1
[18]杨小天．MOCVD法ZnO薄膜生长及其紫外探测器的制备与初步研究．吉林大学博士学位论文．2004-6
[19]Bagnall D M, et al. Optically pumped lasing of ZnO at room temperature. Appl. Phys. Lett., 1997, 70: 2230
[20]Segawa Y, et al. Growth of ZnO thin film by laser MBE:lasing ofexciteon at room temperature. Phys. Stat. Solidi (b), 1997, 202:669
[21]Reynolds D C, et al. Optically pumped ultraviolet lasing from ZnO. Solid State Commun, 1996, 99 (12): 873
[22]Liu Y, Gorla C R, Liang S, et al. Ultraviolet detector based on epitaxial ZnO films grown by MOCVD[J]. J Electronic Mater, 2000,29 (1): 69
[23]Bae S H, et al. Applied Surface Science, 2000, 154-155:458
[24]Schuler T, Aegerter M A. Optical and structural properties of sol-gel ZnO: Al coatings. Thin Solid Films, 1999, 351:125-131
[25]Sliva R F, Zaniquelli M E D. Journal of Non-Crystalline Solides, 1999, 247:248
[26]Zayer N K, et al. Thin Solid Films, 1999, 352:179
[27]Boyang Liu,Guotong Du, Xiaotian Yang, Baijun Zhao, Yuantao Zhang, Hongjun Yang, Jinyue Gao, Dali Liu.Influence of different post-thermal armealing atmosphere on properties of ZnO film grown by metal organic chemical vapor deposition, International Symposium on ZnO and Relative Materials and Devices.
[28]Fu X L, Tan G L, Gordon P, et al. Third-order Nonlinearity Induced Lateral-mode Frequercy Locking and Beam Instability in the High-power Operation of Narrow-ridge Semicondutor Lasers. IEEE Journal of Quantum Electronics. 1998, 38 (4) 1447-1454
[29]Nakanishi Y, Miyake A, Kommami H, et al. Applied Surface Science, 1999, 142:233-236
[30]Kobayashi K, Matsubara T, Matsushima S, et al. Thin Solid Films, 1995,266:106-109
[31]杨洪军，赵佰军，杜国同，杨小天，张源涛，侯小珂，马艳，刘博阳，方秀军，MOCVD法生长ZnO／GaN／Al2O3多层结构，第八届全国MOCVD学术会议论文集
[32]杨南如，余桂郁．溶胶-凝胶法的基本原理与过程[J]．硅酸盐通报，1993(2)：56-63
[33]Jimenez-Gonzalez A E,Jose A, Sotourueta, et al. Optial and Electrical Charateristics of Aluminum-doped ZnO Thin Films Perared by Sol-gel Technique.J Crys Growth. 1998,192:430
[34]巩锋．溶胶凝胶法制备Al3+:ZnO薄膜及其性能研究．北京工业大学工学硕士学位论文，2003．5
[35]Jae Hyoung Chol, et al. Initial preferred growth in zinc oxide thin films on Si and amorphous aubstrates by a pulsed laser deposition.[J]Cryst Growth, 2001, 226:493～500
[36]Mahan G D, Levmson L M, Philipp H R.[J]. J Appl Phys, 1979, 50(4):2799-2812
[37]Eda K[J].J Appl Phys, 54:1090-1099
[38]方开泰．《均匀设计》．北京．科学出版社，1994，4-63，70．
[39]尹德建．正交实验法在工艺设计中的应用．混合微电子技术．1991，2(4)．-8-13，40
[40]Ohyama M, et al. Sol-gel preparation of ZnO films with extremely preferred orientation along (002) plane fromzinc acetate solution. Thin Solid Films, 1997, 306:83
[41]姜胜林等，退火温度对ZnO陶瓷薄膜低压压敏特性的影响，材料研究学报，2005，2：103
[42]王玉平，万云，微量掺铝工艺对氧化锌压敏特性的影响，电磁避雷器，2000，4：42～44
[43]杨南如．无机非金属材料测试方法．武汉工业大学出版社，1993
[44]白春礼．原子和分子的观察和操纵．湖南教育出版社，1999．
[45]刘恩科等．半导体物理学．国防工业出版社，1994
[46]方荣川．固体光谱学．合肥：中国科学技术大学出版社，2001
[2]傅静，徐政，ZnO压敏电阻器的性能及发展，现代技术陶瓷，2004，1：31
[3]黄炎球等，ZnO薄膜及其性能研究进展，无机材料学报，2001．5：16卷，391～397
[4]纪士东等，氧化锌压敏材料研究与发展进展，陶瓷学报，1997，3，第18卷，第1期：52～55
[5]吕建国，叶志镇．ZnO薄膜的最新研究进展．功能材料，2002，33(6)：581～582
[6]李春明等，纳米ZnO材料的制备与应用研究进展，材料导报，2003，5，第17卷，第5期：39～41
[7]陈艺锋等，湿法合成氧化锌压敏电阻粉体的现状与展望，电子元件与材料，2004，1，第1期：23～26
[8]贾桂林，张海军，谭伟。氧化锌薄膜研究的新进展．材料导报，2003，17：207～209
[9]KING S L，GARDENIERS J G E，BOYD I W．Pulsed laser deposited ZnO for device application[J]．Appl Surf Sci 1996,96-98：811-818
[10]陈志清，谢恒堃。氧化锌压敏瓷及其在电力系统中的应用。水利电力出版社
[11]Suzoki Y, Ohki A, Mizutani T, et al.J.Phys. D:Appl.Phys,1987,20:511-517
[12]Horio N, Hiramatsu M, Nawata M, et al.Vacuum,1998,51(4):719-722
[13]贾锐，曲凡钦，武光明等。功能材料，1999，30(6)：636-638
[14]黄焱球，刘梅冬，等。ZnO陶瓷薄膜的制备及其低压压敏特性[J]。压电与声光，2001，23(5)：384-386
[15]King S L，Gardeniers J G E，Boyd I W Pulsed laser deposited ZnO for devices application[J]．Appl Surf Sci，1996,96-98：811
[16]杨邦朝．薄膜物理与技术．高等学校教材
[17]周英．溶胶-凝胶法制备ZnO薄膜．电子科技大学．硕士学位论文．2005-1-1
[18]杨小天．MOCVD法ZnO薄膜生长及其紫外探测器的制备与初步研究．吉林大学博士学位论文．2004-6
[19]Bagnall D M, et al. Optically pumped lasing of ZnO at room temperature. Appl. Phys. Lett., 1997, 70: 2230
[20]Segawa Y, et al. Growth of ZnO thin film by laser MBE:lasing ofexciteon at room temperature. Phys. Stat. Solidi (b), 1997, 202:669
[21]Reynolds D C, et al. Optically pumped ultraviolet lasing from ZnO. Solid State Commun, 1996, 99 (12): 873
[22]Liu Y, Gorla C R, Liang S, et al. Ultraviolet detector based on epitaxial ZnO films grown by MOCVD[J]. J Electronic Mater, 2000,29 (1): 69
[23]Bae S H, et al. Applied Surface Science, 2000, 154-155:458
[24]Schuler T, Aegerter M A. Optical and structural properties of sol-gel ZnO: Al coatings. Thin Solid Films, 1999, 351:125-131
[25]Sliva R F, Zaniquelli M E D. Journal of Non-Crystalline Solides, 1999, 247:248
[26]Zayer N K, et al. Thin Solid Films, 1999, 352:179
[27]Boyang Liu,Guotong Du, Xiaotian Yang, Baijun Zhao, Yuantao Zhang, Hongjun Yang, Jinyue Gao, Dali Liu.Influence of different post-thermal armealing atmosphere on properties of ZnO film grown by metal organic chemical vapor deposition, International Symposium on ZnO and Relative Materials and Devices.
[28]Fu X L, Tan G L, Gordon P, et al. Third-order Nonlinearity Induced Lateral-mode Frequercy Locking and Beam Instability in the High-power Operation of Narrow-ridge Semicondutor Lasers. IEEE Journal of Quantum Electronics. 1998, 38 (4) 1447-1454
[29]Nakanishi Y, Miyake A, Kommami H, et al. Applied Surface Science, 1999, 142:233-236
[30]Kobayashi K, Matsubara T, Matsushima S, et al. Thin Solid Films, 1995,266:106-109
[31]杨洪军，赵佰军，杜国同，杨小天，张源涛，侯小珂，马艳，刘博阳，方秀军，MOCVD法生长ZnO／GaN／Al2O3多层结构，第八届全国MOCVD学术会议论文集
[32]杨南如，余桂郁．溶胶-凝胶法的基本原理与过程[J]．硅酸盐通报，1993(2)：56-63
[33]Jimenez-Gonzalez A E,Jose A, Sotourueta, et al. Optial and Electrical Charateristics of Aluminum-doped ZnO Thin Films Perared by Sol-gel Technique.J Crys Growth. 1998,192:430
[34]巩锋．溶胶凝胶法制备Al3+:ZnO薄膜及其性能研究．北京工业大学工学硕士学位论文，2003．5
[35]Jae Hyoung Chol, et al. Initial preferred growth in zinc oxide thin films on Si and amorphous aubstrates by a pulsed laser deposition.[J]Cryst Growth, 2001, 226:493～500
[36]Mahan G D, Levmson L M, Philipp H R.[J]. J Appl Phys, 1979, 50(4):2799-2812
[37]Eda K[J].J Appl Phys, 54:1090-1099
[38]方开泰．《均匀设计》．北京．科学出版社，1994，4-63，70．
[39]尹德建．正交实验法在工艺设计中的应用．混合微电子技术．1991，2(4)．-8-13，40
[40]Ohyama M, et al. Sol-gel preparation of ZnO films with extremely preferred orientation along (002) plane fromzinc acetate solution. Thin Solid Films, 1997, 306:83
[41]姜胜林等，退火温度对ZnO陶瓷薄膜低压压敏特性的影响，材料研究学报，2005，2：103
[42]王玉平，万云，微量掺铝工艺对氧化锌压敏特性的影响，电磁避雷器，2000，4：42～44
[43]杨南如．无机非金属材料测试方法．武汉工业大学出版社，1993
[44]白春礼．原子和分子的观察和操纵．湖南教育出版社，1999．
[45]刘恩科等．半导体物理学．国防工业出版社，1994
[46]方荣川．固体光谱学．合肥：中国科学技术大学出版社，2001