TiO_2和ZnO纳米薄膜的制备及传感特性
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摘要
近几年来纳米材料的制备及应用一直是纳米研究中的热点。纳米尺寸对所研究的对象产生许多奇异性质，或对原有性质有十分显著的改进和提高，表现出传统材料所不具备的奇异或反常的H物理H、H化学H特性。这种尺寸奇特性质是由表面效应、小尺寸效应、宏观量子隧道效应三大纳米效应所引起的。因此，氧化物纳米材料广泛的应用于湿度传感器、光传感器、新能源、生物医疗等领域。
氧化物TiO_2是宽带隙半导体，主要本征吸收388nm以下的紫外光[19]，可产生光电、光化学效应，是用以制备实用化光伏器件、光催化器件和气体传感器的优选材料。TiO_2纳米薄膜更是较大的比表面积和较强的吸附能力，因此在实现以上功能器件时具有更大的优势。目前基于宽带隙氧化物（如SnO_2、Al_2O_3等）纳米薄膜的湿度传感器研究，引起人们的广泛关注。但是TiO_2纳米薄膜这一方面的应用，目前尚少有报道。基于TiO_2纳米管阵列薄膜的电容式湿度传感器具有突出的优点：体积小、灵敏度高、响应速度快，测量范围宽，信号直接以电参量的形式输出，使用操作方便。由于TiO_2纳米薄膜更大的比表面积和更强的光子捕捉能力，并且具有制作简单、容易掺杂、灵敏度高、稳定性强等优点，所以基于TiO_2纳米材料的紫外传感器在光电子领域应该得到广泛的研究和应用。但是目前该方面国内外尚少有研究。
ZnO纳米材料是另一种备受关注的纳米功能材料，它具有直接宽带隙（Eg=3.37eV）、高激子束缚能（60 meV）、高热导率、易于掺杂等优点，因而在光电子领域引起广泛的关注,在紫外发光（或传感）器件、气体传感器、输运电子器件、表面声波器件等领域极大的应用前景。另外，可以利用过渡金属（Fe、Co、Ni、Mn）掺杂ZnO，制备自旋极化的激光光源，这同样是目前ZnO纳米材料与器件领域研究的热点。我们知道，制备较好ZnO纳米结构薄膜是人们研究ZnO光电子器件的基础。
基于以上考虑，本文围绕纳米材料TiO_2、ZnO的制备及TiO_2纳米管薄膜湿敏、光敏特性研究，主要展开了以下几个方面的研究工作：
（1）利用电化学的方法制备TiO_2纳米薄膜，制备的纳米结构整齐，比表面积大，且制作方法简单。并采用SEM、TEM、Raman等测试手段对TiO_2纳米管阵列的表面形貌、内部微结构、化学键态等进行了表征。分析了TiO_2纳米管阵列形成的基本机理。
(2)利用TiO_2纳米管阵列薄膜制作湿度传感器,测试了其电容对湿度的依赖关系。并在不同电极构型下测其电容随湿度变化而变化的特性,结果发现:梳状电极结构下灵敏度增强,湿滞效应变小。
(3)通过采用不同光源、光照强度、电压来检测TiO_2纳米管阵列薄膜的光敏特性。实验发现:氨化氮掺杂TiO_2纳米管阵列薄膜对于365纳米的紫外光表现出强烈的光敏特性。同样光照条件下,电压越大,则灵敏度越高。
(4)建立了TiO_2纳米管阵列湿敏光敏器件的等效电路,分析了TiO_2纳米管阵列薄膜湿敏光敏器件在外界激励(光照或湿气)下的敏感机理,运用了能带结构理论来分析TiO_2纳米管阵列薄膜对紫外光的敏感特性。
(5)分别采用电化学法和H_2O_2活化的锌粉与活性炭高温热处理的方法来制备ZnO纳米结构,发现后一种方法制备的纳米结构具有方法简单、表面积大等优点。利用SEM对ZnO纳米结构进行初步的表征,发现锌粉与活性炭的质量比越低,纳米结构越好。
The recent years have witnessed the rapid progresses for preparation and applications of nano-materials. Size effects from nanosize materials have impressively changed or improved the properties of original bulk materials, which have introduced many unprecedent terms into the traditional physical and chemical fields, among which the surface effect, small size effect and quantum tunneling effect are most concerned. It unwhelmingly bring forth the new era of nanophysics and nanodevices. So far, many newly emerged opto-electrical (or opto-chemical) devices based on oxide nanomartials such as ZnO and TiO_2, etc, have drawn much concerns worldwide, whose extensive applications include humidity sensor, optical sensor, new energy source and bio-medical science, and so on.
Titannium dioxide (TiO_2) is a wide-band-gap semiconductor (Anatase: Eg=3.2eV, Rutile: Eg=3.0eV) , whose intrinsic light absorption band is in ultraviolet region with center wavelength of ~388 nm. It is beneficial to bring forth opto-electric effect or opto-chemical effect, which indicates TiO_2 is a promising material for fabrication of photovoltaics devices,photocatalysis devices,gas sensor. Morever, TiO_2 films with nanosize structure, show larger surface-volume ratio (aspect ratio) and superior adsorption ability, which prefigures the advantage of TiO_2 films with nanosize structure for application in abovementioned fields, in comparison with the bulk conuterpart. Nowadays, humidity sensor based on wide bandgap semiconductor film with nanostructure, such as SnO_2 and Al2O3, have been intensively studied, but this kind study is seldom carried on TiO_2. In our present view, humidity capacitive sensor based on TiO_2 film with nanostructure should show such outstanding advantages as small size, high sensitivity, rapid response, wide sensing region, direct electrical output, and convenient manipulation. Due to the larger aspect ratio and stronger photon adsorption capacity of TiO_2 films with nanosize structure, it is no doubt to see its promising application in opto-electronics as ultraviolet sensor, let alone its other advantages as simple fabrication procedure, easy doping, high sensitivity, high stability, etc.
Znic oxide (ZnO) is another kind wide-band-gap semiconductor that has been greatly concerned. It shows many unique properties of direct bandgap of 3.37 eV, high exciton binding energy of 60 meV, high thermal conductance, and easy doping, wich makes it a promising candidate to be applied in fields of ultraviolet (UV) light emitters, gas sensors, transparent electronics, and surface acoustic wave devices. In adition, ZnO can be doped with transitional metal (Fe, Co, Ni, Mn), which is vital for fabrication of spin functional devices such as spin-polaried laser, which is also a intensively concerned study branch of ZnO. All in all, we should bear in mind that the preparation of ZnO with optimal microstructure is essential for realization of abovementioned devices.
According to above consideratioin, this thesis is mainly organized on the preparation of TiO_2 and ZnO nanostructute films, followed by their application as humiditity sensor and ultraviolet sensor. The detailed works are spread out as follows:
(1)TiO_2 nanotube films are fabricated by using electro-chemical method. As prepared nanotube films with high-aspect-ratio are well perpendicularly aligned on the Ti foil. The surface morphology, microstructure and chemical bonding states are characterized by means of SEM, TEM, and Raman spectroscopy. The formation mechanism of TiO_2 nanotube films is also studied.
(2)Capacitive humidity sensor based on as-prepared TiO_2 nanotube films are fabricated, and its capacitance dependences on envirometal humidity and temperature are studied. Measuremnts are also performed on as-frmed sensor with different configuration of electrodes, namely dot electrod and comb-like electrod, which indicates humidity sensing properties are well enhanced (higher sensitivity and lower humidity hysterisis)using comb-like electrod.
(3)Ultroviolet light sensor based on aminated TiO_2 nanotube films are fabricated, and the light sensing properties are studied at different experimental parameters of light wavelength, light strength, bias voltage. It is shown as-formed sensors show most optimal sensing properties at light excitation with wavelength at 365 nm. At simultaneous light excitation, the higher the biased voltage, and the higher sensor sensitivity.
(4)The equivalent circuit of as-fabricated TiO_2 nanotube films humidity sensor is established based on our electrical measurement configuration, the humidity sensing mechanism at environmetal stimulation is analyzed. Especially the ultraviolet light sensing properties is analyzed by employing erengy band theory. (5)ZnO nanostructures are respectively formed by two different methods, namely the anodization method and the thermal growth method. It is shown by using the later method ZnO namostructure will be formed with advantages of easy fabrication procedure and large aspect ratio. By characterization of SEM, it is found the lower the mass ratio of Zn to C powder, the better the morphology of as-formed ZnO nanoneedles.
氧化物TiO_2是宽带隙半导体，主要本征吸收388nm以下的紫外光[19]，可产生光电、光化学效应，是用以制备实用化光伏器件、光催化器件和气体传感器的优选材料。TiO_2纳米薄膜更是较大的比表面积和较强的吸附能力，因此在实现以上功能器件时具有更大的优势。目前基于宽带隙氧化物（如SnO_2、Al_2O_3等）纳米薄膜的湿度传感器研究，引起人们的广泛关注。但是TiO_2纳米薄膜这一方面的应用，目前尚少有报道。基于TiO_2纳米管阵列薄膜的电容式湿度传感器具有突出的优点：体积小、灵敏度高、响应速度快，测量范围宽，信号直接以电参量的形式输出，使用操作方便。由于TiO_2纳米薄膜更大的比表面积和更强的光子捕捉能力，并且具有制作简单、容易掺杂、灵敏度高、稳定性强等优点，所以基于TiO_2纳米材料的紫外传感器在光电子领域应该得到广泛的研究和应用。但是目前该方面国内外尚少有研究。
ZnO纳米材料是另一种备受关注的纳米功能材料，它具有直接宽带隙（Eg=3.37eV）、高激子束缚能（60 meV）、高热导率、易于掺杂等优点，因而在光电子领域引起广泛的关注,在紫外发光（或传感）器件、气体传感器、输运电子器件、表面声波器件等领域极大的应用前景。另外，可以利用过渡金属（Fe、Co、Ni、Mn）掺杂ZnO，制备自旋极化的激光光源，这同样是目前ZnO纳米材料与器件领域研究的热点。我们知道，制备较好ZnO纳米结构薄膜是人们研究ZnO光电子器件的基础。
基于以上考虑，本文围绕纳米材料TiO_2、ZnO的制备及TiO_2纳米管薄膜湿敏、光敏特性研究，主要展开了以下几个方面的研究工作：
（1）利用电化学的方法制备TiO_2纳米薄膜，制备的纳米结构整齐，比表面积大，且制作方法简单。并采用SEM、TEM、Raman等测试手段对TiO_2纳米管阵列的表面形貌、内部微结构、化学键态等进行了表征。分析了TiO_2纳米管阵列形成的基本机理。
(2)利用TiO_2纳米管阵列薄膜制作湿度传感器,测试了其电容对湿度的依赖关系。并在不同电极构型下测其电容随湿度变化而变化的特性,结果发现:梳状电极结构下灵敏度增强,湿滞效应变小。
(3)通过采用不同光源、光照强度、电压来检测TiO_2纳米管阵列薄膜的光敏特性。实验发现:氨化氮掺杂TiO_2纳米管阵列薄膜对于365纳米的紫外光表现出强烈的光敏特性。同样光照条件下,电压越大,则灵敏度越高。
(4)建立了TiO_2纳米管阵列湿敏光敏器件的等效电路,分析了TiO_2纳米管阵列薄膜湿敏光敏器件在外界激励(光照或湿气)下的敏感机理,运用了能带结构理论来分析TiO_2纳米管阵列薄膜对紫外光的敏感特性。
(5)分别采用电化学法和H_2O_2活化的锌粉与活性炭高温热处理的方法来制备ZnO纳米结构,发现后一种方法制备的纳米结构具有方法简单、表面积大等优点。利用SEM对ZnO纳米结构进行初步的表征,发现锌粉与活性炭的质量比越低,纳米结构越好。
The recent years have witnessed the rapid progresses for preparation and applications of nano-materials. Size effects from nanosize materials have impressively changed or improved the properties of original bulk materials, which have introduced many unprecedent terms into the traditional physical and chemical fields, among which the surface effect, small size effect and quantum tunneling effect are most concerned. It unwhelmingly bring forth the new era of nanophysics and nanodevices. So far, many newly emerged opto-electrical (or opto-chemical) devices based on oxide nanomartials such as ZnO and TiO_2, etc, have drawn much concerns worldwide, whose extensive applications include humidity sensor, optical sensor, new energy source and bio-medical science, and so on.
Titannium dioxide (TiO_2) is a wide-band-gap semiconductor (Anatase: Eg=3.2eV, Rutile: Eg=3.0eV) , whose intrinsic light absorption band is in ultraviolet region with center wavelength of ~388 nm. It is beneficial to bring forth opto-electric effect or opto-chemical effect, which indicates TiO_2 is a promising material for fabrication of photovoltaics devices,photocatalysis devices,gas sensor. Morever, TiO_2 films with nanosize structure, show larger surface-volume ratio (aspect ratio) and superior adsorption ability, which prefigures the advantage of TiO_2 films with nanosize structure for application in abovementioned fields, in comparison with the bulk conuterpart. Nowadays, humidity sensor based on wide bandgap semiconductor film with nanostructure, such as SnO_2 and Al2O3, have been intensively studied, but this kind study is seldom carried on TiO_2. In our present view, humidity capacitive sensor based on TiO_2 film with nanostructure should show such outstanding advantages as small size, high sensitivity, rapid response, wide sensing region, direct electrical output, and convenient manipulation. Due to the larger aspect ratio and stronger photon adsorption capacity of TiO_2 films with nanosize structure, it is no doubt to see its promising application in opto-electronics as ultraviolet sensor, let alone its other advantages as simple fabrication procedure, easy doping, high sensitivity, high stability, etc.
Znic oxide (ZnO) is another kind wide-band-gap semiconductor that has been greatly concerned. It shows many unique properties of direct bandgap of 3.37 eV, high exciton binding energy of 60 meV, high thermal conductance, and easy doping, wich makes it a promising candidate to be applied in fields of ultraviolet (UV) light emitters, gas sensors, transparent electronics, and surface acoustic wave devices. In adition, ZnO can be doped with transitional metal (Fe, Co, Ni, Mn), which is vital for fabrication of spin functional devices such as spin-polaried laser, which is also a intensively concerned study branch of ZnO. All in all, we should bear in mind that the preparation of ZnO with optimal microstructure is essential for realization of abovementioned devices.
According to above consideratioin, this thesis is mainly organized on the preparation of TiO_2 and ZnO nanostructute films, followed by their application as humiditity sensor and ultraviolet sensor. The detailed works are spread out as follows:
(1)TiO_2 nanotube films are fabricated by using electro-chemical method. As prepared nanotube films with high-aspect-ratio are well perpendicularly aligned on the Ti foil. The surface morphology, microstructure and chemical bonding states are characterized by means of SEM, TEM, and Raman spectroscopy. The formation mechanism of TiO_2 nanotube films is also studied.
(2)Capacitive humidity sensor based on as-prepared TiO_2 nanotube films are fabricated, and its capacitance dependences on envirometal humidity and temperature are studied. Measuremnts are also performed on as-frmed sensor with different configuration of electrodes, namely dot electrod and comb-like electrod, which indicates humidity sensing properties are well enhanced (higher sensitivity and lower humidity hysterisis)using comb-like electrod.
(3)Ultroviolet light sensor based on aminated TiO_2 nanotube films are fabricated, and the light sensing properties are studied at different experimental parameters of light wavelength, light strength, bias voltage. It is shown as-formed sensors show most optimal sensing properties at light excitation with wavelength at 365 nm. At simultaneous light excitation, the higher the biased voltage, and the higher sensor sensitivity.
(4)The equivalent circuit of as-fabricated TiO_2 nanotube films humidity sensor is established based on our electrical measurement configuration, the humidity sensing mechanism at environmetal stimulation is analyzed. Especially the ultraviolet light sensing properties is analyzed by employing erengy band theory. (5)ZnO nanostructures are respectively formed by two different methods, namely the anodization method and the thermal growth method. It is shown by using the later method ZnO namostructure will be formed with advantages of easy fabrication procedure and large aspect ratio. By characterization of SEM, it is found the lower the mass ratio of Zn to C powder, the better the morphology of as-formed ZnO nanoneedles.
引文
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2 Wakai F, Sakaguchi S, Matsuno Y, Adv. Ceram. Mater, 1986, 1(3):259
3吴锦雷.纳米光电功能薄膜.北京大学出版社, 2006:13-14, 109-110
4胡安正.纳米科技与纳米材料的应用研究.郧阳师范高等专科学校学报. 2005, 25(6):40-41
5于向阳,梁文,杜永娟等.二氧化钛光催化材料的应用进展[J].材料导报.2000, 24(2):101
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