CN110364583B - TiO2薄膜的制备方法、光电探测器件及其制备方法 - Google Patents
TiO2薄膜的制备方法、光电探测器件及其制备方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 20
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Abstract
本发明公开了一种TiO2薄膜的制备方法、光电探测器件及其制备方法，涉及光电检测技术领域。本发明利用在含氧环境下煅烧ALD(原子层逐层沉积的方法)制得的TiO2薄膜，一方面使得TiO2薄膜由非晶向局部单晶转变，形成鱼鳞状的外貌；另一方面减少氧缺陷，降低了材料中电子的浓度，降低光生载流子的复合，利于形成光电流，同时还降低了暗电流的大小；由此材料制得的光电探测器件使得器件提升了光电探测的性能；让器件具备了栅极电压调控光谱响应的能力。
Description
技术领域
本发明涉及光电检测技术领域，尤其涉及一种TiO2薄膜的制备方法、光电探测器件及其制备方法。
背景技术
在现代光电探测技术中，光电探测器可以在很多领域可以找到相关应用，其中包括环境安全、信息技术、医疗、天文观测和军事应用以及卫星通讯等。成为继激光探测技术和红外探测技术之后，紫外波段也越来越受到人们的关注，发展起来的又一种极其重要的光电探测技术。国外已开始紫外技术的军用研究，并己经取得一定的进展，比如紫外制导、紫外预警、紫外干扰以及紫外通讯等。金属的氮化物和氧化物常被用来作为宽禁带半导体，如TiO2等宽禁带半导体材料，化学性质稳定，而且在紫光和近紫外区有很好吸收，对可见光透明，是光电检测中紫外检测理想的半导体，尤其是在宽光谱响应方面可作为顶层材料而不影响底层材料对可见光、红外光的检测。目前已经报道了通过化学气相沉积，脉冲激光沉积，溅射和水热法等方法制备了金属氧化物的各种纳米结构，已有很多文献报道了金属氧化物、氮化物、硫化物在光电探测中的应用。
氧化钛(TiO2)由于其高折射率，优异的电性能和良好的化学稳定性，在太阳能电池、光催化反应、LED、光电探测器等领域引起了广泛关注。同时也是光电检测中紫外检测理想的半导体。目前通过化学气相沉积，脉冲激光沉积，溅射和水热法等方法可制备TiO2的各种纳米结构。金红石相的TiO2具有3.0eV的直接光学带隙，而TiO2的锐钛矿相具有3.2eV的间接光学带隙。未掺杂TiO2纳米材料由于存在氧空位的浅施主，而显示为n型掺杂。
基于绝缘栅型金属-半导体-金属(MSM)结构的探测器具有量子效率高、开关比大、热稳定性高等优点。半导体纳米线、纳米管薄膜型绝缘栅场效应 (MOSFET)晶体管在光电探测领域的应用更是得到了拓展。通过栅极电压可调控TiO2的沟道载流子分布以及耗尽层特性，提升器件对紫外光探测能力。
然而，使用现有的制备方法制得的TiO2薄膜材料多是非晶材料或者是多晶材料，难以获得TiO2单晶薄膜，因此制备的光电探测器件性能较弱，不能具备调控光谱响应的能力。
发明内容
本发明所要解决的技术问题是背景技术中提到的问题，通过制备出TiO2单晶薄膜材料，降低材料中电子浓度，以提升光电器件的探测性能。
为了解决上述问题，本发明提出以下技术方案：
第一方面，本发明提出一种TiO2薄膜的制备方法，包括以下步骤：
S1，以氮气作为负载气体，交替通入钛源和水蒸气，在衬底的氧化层上得到反应生成的原子层级别的TiO2，反应温度为220～300℃，反应压强为10～20帕；
S2，将S1得到的有TiO2的衬底在含氧气氛下煅烧，煅烧温度为400～800℃，即在衬底上制得TiO2薄膜；
其中，所述钛源为异氧丙醇钛，钛源的温度为70～80℃；
所述衬底为一面含有氧化硅层，另一面为Si的P型Si。
其进一步的技术方案为，所述步骤S1中，还包括去除前驱体的步骤，所述前驱体为异氧丙醇钛和水蒸气。
其进一步的技术方案为，所述步骤S1中，所述通入氮气作为负载气体的钛源和水蒸气的具体步骤为，
依次将通入钛源和水蒸气，分别去除前驱体作为一个循环，重复200～300个循环。
其进一步的技术方案为，每次循环氮气作为负载气体的钛源通入时间为0.1～0.5s，流速为5.0～10.0sccm。
其进一步的技术方案为，每次循环氮气作为负载气体的水蒸气通入时间为 0.1～0.5s，流速为5.0～10.0sccm。
其进一步的技术方案为，每次循环去除前驱体时间为20～40s。
其进一步的技术方案为，还包括对衬底的预处理步骤，所述预处理步骤为将衬底表面的有机物、金属离子及洗涤残留物洗净，干燥。
第二方面，本发明提出一种光电探测器件，包括TiO2薄膜，所述TiO2薄膜由第一方面所述的TiO2薄膜的制备方法制得。
第三方面，本发明提出一种如第二方面所述的光电探测器件的制备方法，包括以下步骤：
在所述衬底含有TiO2薄膜的一面制备场效应晶体管的源极和漏级，所述源极和漏级之间的沟道宽度为10～75微米；
去除衬底另一面因步骤S2煅烧产生的氧化硅，制备栅极，即得所述光电探测器件。
与现有技术相比，本发明所能达到的技术效果包括：
本发明利用在含氧环境下煅烧ALD(原子层逐层沉积的方法)制得的TiO2薄膜，一方面使得TiO2薄膜由非晶向局部单晶转变，形成鱼鳞状的外貌；另一方面减少氧缺陷，降低了材料中电子的浓度，降低光生载流子的复合，利于形成光电流；由此材料制得的光电探测器件使得器件提升了光电探测的性能；让器件具备了栅极电压调控光谱响应的能力。
附图介绍
图1为基于本发明实施例制得的TiO2薄膜材料的MOSFET结构光电检测器件结构的模型；
图2为本发明一实施例制得的光电探测器件上表面的光学照片；
图3为本发明一实施例制备步骤S2煅烧后，制得的结晶化鱼鳞状TiO2薄膜材料的表现出来的鱼鳞结构；
图4为步骤S2煅烧前后的TiO2薄膜材料的XRD表征；
图5为比较例的光电器件在不同栅压下光电流的光谱响应；
图6为实施例的光电器件在不同栅压下光电流的光谱响应。
具体实施方式
下面将通过以下实施例进行清楚、完整地描述本发明的技术方案中显然，以下将描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
应当理解，当在本说明书和所附权利要求书中使用时，术语“包括”和“包含”指示所描述特征、整体、步骤、操作、元素和/或组件的存在，但并不排除一个或多个其它特征、整体、步骤、操作、元素、组件和/或其集合的存在或添加。
还应当理解，在此本发明实施例说明书中所使用的术语仅仅是出于描述特定实施例的目的而并不意在限制本发明实施例。如在本发明实施例说明书和所附权利要求书中所使用的那样，除非上下文清楚地指明其它情况，否则单数形式的“一”、“一个”及“该”意在包括复数形式。
本发明实施例提出一种结晶化TiO2薄膜的制备方法，包括以下步骤：
S1，以氮气作为负载气体，交替通入钛源和水蒸气，在衬底的氧化层上得到反应生成的原子层级别的TiO2，反应温度为220～300℃，反应压强为10～20帕；
S2，将S1得到的有TiO2的衬底在含氧气氛下煅烧，煅烧温度为400～800℃，即在衬底上制得结晶化鱼鳞状的TiO2薄膜，如图3所示；
其中，所述钛源为异氧丙醇钛(Ti{OCH(CH3)2}4)，钛源的温度为70～80℃；
所述衬底为一面含有氧化硅层，另一面为Si的P型Si。
在一实施例中，以氩气作为负载气体，引入钛源和水蒸气。
参见图3，未退火之前，衬底上得到的TiO2受基底的影响为非晶态，经煅烧退火后，由非晶态转为局部单晶态，形成了类似鱼鳞一样的形貌，其光电探测性能也得到提升。
参见图4，其为步骤S2煅烧前后的TiO2薄膜材料的XPS表征。其中a为步骤S2煅烧前的TiO2薄膜材料的XPS表征；b为步骤S2煅烧后的TiO2薄膜材料的XPS表征。
由图可知，步骤S2煅烧前无明显的氧化钛的特征峰说明氧化钛为非晶态，经过步骤S2煅烧后氧化钛的特征峰出现，说明氧化钛薄膜已结晶化。
在一实施例中，步骤S1还包括去除前驱体的步骤，所述前驱体为异氧丙醇钛和水蒸气。通过及时去除前驱体，促使反应不断进行，使得在衬底上得到原子层级别的TiO2。
在一实施例中，所述步骤S1中，所述通入氮气作为负载气体的钛源和水蒸气的具体步骤为，依次将通入钛源和水蒸气，分别去除前驱体作为一个循环，重复200～300个循环。
具体地，反应时，先交替通入氮气作为负载气体的钛源和水蒸气，使其充分在衬底的氧化层上进行反应，接着去除未反应的异氧丙醇钛和水蒸气，再交替通入氮气作为负载气体的钛源和水蒸气……，由此重复循环，通过重复通入钛源和水蒸气、去除前驱体的循环，使得在衬底上逐层累计，不断得到反应生成的TiO2。
每次循环氮气作为负载气体的钛源通入时间为0.1～0.5s，流速为 5.0～10.0sccm。
每次循环氮气作为负载气体的水蒸气通入时间为0.1～0.5s，流速为 5.0～10.0sccm。
每次循环去除前驱体时间为20～40s。
在一实施例中，步骤S2煅烧时，通过升温200～400分钟，将温度升至 400～800℃，保温200～400分钟。
例如，在一实施例中，将衬底有SiO2层面朝上，放入原子层沉积反应腔体中，使用氮气为负载气体，将异氧丙醇钛Ti{OCH(CH3)2}4作为钛源，在腔体里交替通入钛源和水蒸气0.1～0.5s，去除前驱体20～40s，后再交替通入钛源和水蒸气0.1～0.5s，去除前驱体20～40s……以此循环，200～300个循环，得到在衬底 SiO2/P-Si上生长的TiO2；将有TiO2的SiO2/P-Si衬底，放在马弗炉中，在空气环境下煅烧，煅烧温度为400～800℃，即制得TiO2薄膜。
本实施例利用在含氧环境下煅烧ALD(原子层逐层沉积的方法)制得的TiO2薄膜，一方面使得TiO2薄膜由非晶向局部单晶转变，形成鱼鳞状的外貌；另一方面减少氧缺陷，降低了材料中电子的浓度，降低光生载流子的复合，利于形成光电流。
在一实施例中，还包括对衬底的预处理步骤，所述预处理步骤为将衬底表面的有机物、金属离子及洗涤残留物洗净，干燥。
例如，首先利用电子清洗剂稀释液、乙醇、去离子水对衬底进行初步煮洗；
然后用氨水、双氧水和去离子水混合溶液超声清洗衬底表面的有机物，其中，氨水、双氧水和去离子水的体积比值为1:1:5；
用去离子水多次超声清洗去除洗涤残留物；
接着用浓盐酸、双氧水、去离子水溶液超声清除衬底表面的金属离子，其中，浓盐酸、双氧水、去离子水的体积比值为1:1:5；
利用去离子水反复超声清洗去除洗涤残留物；
最后将衬底用氮气吹干后放入真空保温箱保存待用。
需要说明的是，衬底使用超声清洗时间为20～30分钟，水温为60℃，超声清洗可以提高清洗效率。
如上述实施例所述的结晶化TiO2薄膜的制备方法制得的结晶化鱼鳞状TiO2薄膜的应用，所述结晶化鱼鳞状TiO2薄膜可用于制备光电器件。
一种使用上述实施例制得的结晶化鱼鳞状TiO2薄膜制备光电探测器件的方法，包括以下步骤：
在所述衬底含有TiO2薄膜的一面制备场效应晶体管的源极和漏级，所述源极和漏级之间的沟道宽度为10～75微米；电极材料为Au/Cr合金，Au，Ag或 Cu；
去除衬底另一面因步骤S2煅烧产生的氧化硅，镀Au/Cr合金，Au，Ag或 Cu作为栅极，即得所述光电探测器件。
参见图1其为基于本发明实施例制得的TiO2材料的MOSFET结构光电检测器件结构的模型。
参见图2，本发明另一实施例制得的光电探测器件表面的光学照片，由图可知源极(左边区域)、漏极(右边区域)的宽度为1000微米，中间是长度50微米的沟道区。
在一实施例中，利用化学腐蚀法去除衬底另一面因步骤S2煅烧产生的氧化硅。
本发明实施例由制得的结晶化鱼鳞状TiO2薄膜来制备光电器件，使得器件提升了光电探测的性能；让器件具备了栅极电压调控光谱响应的能力。
比较实验
比较例1：衬底的预处理：先对衬底SiO2/P-Si准备和清洗。首先利用电子清洗剂稀释液、乙醇、去离子水进行初步煮洗；然后用氨水、双氧水和去离子水按照1:1:5的比率形成混合溶液，将硅片放入混合液中进行超声清洗15分钟，之后用去离子水多次超声清洗去除洗涤残留物，直至洗完后的洗涤液用PH试纸检测为中性为止；接着用浓盐酸、双氧水、去离子水按照1:1:5的比率形成混合溶液，将硅片放入混合液中进行超声清洗15分钟，之后用去离子水多次超声清洗去除洗涤残留物，直至洗完后的洗涤液用PH试纸检测为中性为止；最后氮气吹干后放入真空保温箱保存待用。
将准备好的衬底有氧化层面朝上，放入原子层沉积反应腔体中，反应腔体中的温度维持在250℃，压强维持在11帕之间。使用氮气为负载气体，将异氧丙醇钛Ti{OCH(CH3)2}4加热至80℃，作为钛源。每一循环腔体里交替引入钛源和水蒸气各0.3秒，再去除前驱体30秒，由此进行不断循环，圈数为300圈，得到在衬底SiO2/P-Si上生长的TiO2，放入低于400℃的马弗炉中煅烧，在衬底表面制得非晶态的TiO2。
将制得非晶态的TiO2的衬底，利用沟道为50微米掩膜板覆盖放入热蒸发炉中，在TiO2表面制备场效应晶体管的源极和漏级，电极材料采用厚度为100纳米的Au/Cr合金，利用化学腐蚀法去除衬底背面P-Si上因煅烧产生的薄层SiO2，在背面镀Ag材料作为栅极，从而制备成功绝缘栅调节型TiO2薄膜的紫外光电探测器件。光电流响应特性如图5所示，源极和漏级之间加的电压为3伏；栅极从-8V变化至8V，间隔为4V；光电流随光谱的响应。器件明显响应于紫外波段，但无明显栅压调控能力，电流的数量级在纳安量级不利于实际应用。
实验例：衬底的预处理：先对衬底SiO2/P-Si准备和清洗。首先利用电子清洗剂稀释液、乙醇、去离子水进行初步煮洗；然后用氨水、双氧水和去离子水按照1:1:5的比率形成混合溶液，将硅片放入混合液中进行超声清洗15分钟，之后用去离子水多次超声清洗去除洗涤残留物，直至洗完后的洗涤液用PH试纸检测为中性为止；接着用浓盐酸、双氧水、去离子水按照1:1:5的比率形成混合溶液，将硅片放入混合液中进行超声清洗15分钟，之后用去离子水多次超声清洗去除洗涤残留物，直至洗完后的洗涤液用PH试纸检测为中性为止；最后氮气吹干后放入真空保温箱保存待用。
将准备好的衬底有氧化层面朝上，放入原子层沉积反应腔体中，反应腔体中的温度维持在250℃，压强维持在11帕之间。使用氮气为负载气体，将异氧丙醇钛Ti{OCH(CH3)2}4加热至80℃，作为钛源。每一循环腔体里交替引入钛源和水蒸气各0.3秒，再去除前驱体30秒，由此进行不断循环，圈数为300圈，得到在衬底SiO2/P-Si上生长的TiO2。
将生长有TiO2的SiO2/P-Si衬底，放在马弗炉中，在空气环境下煅烧，升温速度为每小时200℃，煅烧温度为700℃，保温时间为4小时，后自然冷却至室温，制得结晶化的TiO2薄膜；
将煅烧退火后的TiO2薄膜的衬底，利用沟道为50微米掩膜板覆盖放入热蒸发炉中，在TiO2薄膜表面制备场效应晶体管的源极和漏级，电极材料采用厚度为100纳米的Au/Cr合金，利用化学腐蚀法去除衬底背面P-Si上因煅烧产生的薄层SiO2，在背面镀Ag材料作为栅极，从而制备成功绝缘栅调节型TiO2薄膜的紫外光电探测器件。
光电流响应特性如图6所示，源极和漏级之间加的电压为3伏；栅极从-8V 变化至8V，间隔为4V；光电流随光谱的响应。器件明显响应于紫外波段(<350 纳米)；且明显表现出栅压调控能力，在正的栅压调控下器件的探测能力得到了加强；电流的数量级在微安量级，对辅助电路的要求不高，利于小型化、可穿戴设备的制备。
在上述实施例中，对各个实施例的描述都各有侧重，某个实施例中没有详细描述的部分，可以参见其他实施例的相关描述。
以上所述，为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到各种等效的修改或替换，这些修改或替换都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以权利要求的保护范围为准。
Claims (8)
1.一种光电探测器件的制备方法，其特征在于，所述光电探测器件含有TiO2薄膜，所述光电探测器件的制备方法包括以下步骤：
将煅烧退火后的TiO2薄膜的衬底，利用沟道为50微米掩膜板覆盖放入热蒸发炉中，在衬底含有TiO2薄膜的一面制备场效应晶体管的源极和漏级，所述源极和漏级之间的沟道宽度为50微米；电极材料为Au/Cr合金；
去除衬底另一面产生的氧化硅，再镀制栅极，即得所述光电探测器件；
所述TiO2薄膜的制备方法，包括以下步骤：
S1，以氮气作为负载气体，交替通入钛源和水蒸气，在衬底的氧化层上得到反应生成的原子层级别的TiO2，反应温度为250～300℃，反应压强为11帕；
S2，将S1得到的有TiO2的衬底在含氧气氛下煅烧，煅烧温度为700～800℃，即在衬底上制得结晶化鱼鳞状的TiO2薄膜；
其中，所述钛源为异氧丙醇钛，钛源的温度为80℃；
所述衬底为一面含有氧化硅层，另一面为Si的P型Si。
2.如权利要求1所述的光电探测器件的制备方法，其特征在于，所述步骤S1中，还包括去除前驱体的步骤，所述前驱体为异氧丙醇钛和水蒸气。
3.如权利要求2所述的光电探测器件的制备方法，其特征在于，所述步骤S1中，所述通入氮气作为负载气体的钛源和水蒸气的具体步骤为，
依次将通入钛源和水蒸气，分别去除前驱体作为一个循环，重复200～300个循环。
4.如权利要求3所述的光电探测器件的制备方法，其特征在于，每次循环氮气作为负载气体的钛源通入时间为0.1～0.5s，流速为5.0～10.0sccm。
5.如权利要求3所述的光电探测器件的制备方法，其特征在于，每次循环氮气作为负载气体的水蒸气通入时间为0.1～0.5s，流速为5.0～10.0sccm。
6.如权利要求3所述的光电探测器件的制备方法，其特征在于，每次循环去除前驱体时间为20～40s。
7.如权利要求1所述的光电探测器件的制备方法，其特征在于，还包括对衬底的预处理步骤，所述预处理步骤为将衬底表面的有机物、金属离子及洗涤残留物洗净，干燥。
8.一种光电探测器件，其特征在于，由权利要求1-7任一项所述的光电探测器件的制备方法制得。
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| CN103638915A (zh) * | 2013-12-16 | 2014-03-19 | 复旦大学 | 一种高催化性质TiO2纳米粉末/多孔材料及其制备方法和应用 |
| CN105118919A (zh) * | 2015-07-23 | 2015-12-02 | 苏州大学 | 利用有序排列的二氧化钛小球构成的钙钛矿太阳能电池及其制备方法 |
| CN105575964A (zh) * | 2015-12-22 | 2016-05-11 | 苏州大学 | 结合太阳能电池和光探测器的自驱动光电探测体系及其制备方法 |
| CN106268903A (zh) * | 2016-07-22 | 2017-01-04 | 南京大学 | 一种基于ald技术的表面氮改性二氧化钛纳米颗粒的可见光催化剂的制备方法 |
| CN109148640A (zh) * | 2018-09-28 | 2019-01-04 | 河南大学 | 一种多孔有源层场效应紫外探测器及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103638915A (zh) * | 2013-12-16 | 2014-03-19 | 复旦大学 | 一种高催化性质TiO2纳米粉末/多孔材料及其制备方法和应用 |
| CN105118919A (zh) * | 2015-07-23 | 2015-12-02 | 苏州大学 | 利用有序排列的二氧化钛小球构成的钙钛矿太阳能电池及其制备方法 |
| CN105575964A (zh) * | 2015-12-22 | 2016-05-11 | 苏州大学 | 结合太阳能电池和光探测器的自驱动光电探测体系及其制备方法 |
| CN106268903A (zh) * | 2016-07-22 | 2017-01-04 | 南京大学 | 一种基于ald技术的表面氮改性二氧化钛纳米颗粒的可见光催化剂的制备方法 |
| CN109148640A (zh) * | 2018-09-28 | 2019-01-04 | 河南大学 | 一种多孔有源层场效应紫外探测器及其制备方法 |
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