CN109675542A - 利用pn结自供电的半导体光电催化器件 - Google Patents
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Abstract
利用PN结自供电的半导体光电催化器件属于光电催化技术领域。现有技术为了提高半导体光电催化器件的催化效率，致使结构复杂。本发明之利用PN结自供电的半导体光电催化器件其特征在于，在P‑N+硅片的P‑区分布若干栅条，自P‑区至N+区掺杂浓度由稀变浓，栅条以下的P‑区厚度为50～120μm；栅条的顶面和侧面覆盖有半导体纳米线光电催化层。本发明能够用来催化净化水体，同时能够利用光照实现自供电，催化效率得到提高，器件结构得到简化。
Description
技术领域
本发明涉及一种利用PN结自供电的半导体光电催化器件，能够用来催化净化水体，同时能够利用光照实现自供电，提高催化效率，属于光电催化技术领域。
背景技术
半导体光电催化技术始于1972年问世的TiO2(二氧化钛)催化污水的净化。该技术将TiO2薄膜作为电极，在光照的条件下发生光解水反应，以此发挥催化作用。之后，半导体能带理论被用于解释TiO2光催化机制，当入射的光子能量大于TiO2半导体禁带宽度时，位于价带的电子会跃迁到导带，电子成为具有还原性的高活性电子，同时在价带上产生带正电的具有氧化性的空穴。不过，在电子和空穴会向表面迁移的过程中，一部分电子和空穴会发生体内复合，并且，载流子复合率较高，导致TiO2光催化效率降低。人们发现ZnO、WO3、CdS、ZnS等也都可以作为半导体光催化材料使用，但是，载流子复合率同样较高，而且往往高于TiO2。现有技术通过TiO2改性来降低载流子复合率，提高量子效率。改性措施包括减小晶粒粒度、选择合适的晶型、沉积贵金属、使半导体复合、电化学与光催化相结合等。实验结果表明，电化学与光催化相结合，也就是光电催化能够显著提升反应中的量子效率，进而提高催化效率。
以TiO2为例，实现光电催化先要制作TiO2光电阳极，如悬浮态光电阳极、固定化膜光电阳极以及透明固定化膜光电阳极等，由外部电路加偏置电压，以使电子更加容易离开TiO2表面，从而提高催化效率。如制作TiO2固定化膜光电阳极，引线接外部电源，加10～1000mV的偏置偏压，用于降解苯酚，催化效率能够提高20％以上。然而，制作薄膜光电阳极，外接电源提供偏置电压，这使得光电催化器件结构变得复杂，还需要额外耗费能量，再有就是薄膜状态的催化材料的催化面积有限，而且容易失活。
发明内容
为了在提高催化效率的前提下，简化半导体光电催化器件的结构，绿色节能，进一步加大催化面积，延长光电催化材料的寿命，我们发明了一种利用PN结自供电的半导体光电催化器件。
本发明之利用PN结自供电的半导体光电催化器件，其特征在于，如图1、图2所示，在P-N+硅片的P-区分布若干栅条1，自P-区至N+区掺杂浓度由稀变浓，栅条1以下的P-区厚度为50～120μm；栅条1的顶面和侧面覆盖有半导体纳米线光电催化层2。
本发明其技术效果在于，将本发明之半导体光电催化器件置于待催化净化水体中，如图2所示，当有光自栅条1一侧照射该半导体光电催化器件时，与水体接触的半导体纳米线光电催化层2发挥其光电催化作用，由此实现水体净化；栅条1顶面和两个侧面覆盖了半导体纳米线光电催化层2，这一特点已使催化材料与水体的接触面积增大，相比于现有薄膜状态的催化材料，纳米线光电催化层与水体的接触面积进一步大幅增加，而且不易失活寿命长。同时，光线还照射到P-N+结，上稀下浓渐变掺杂的P-N+硅片有助于快速产生电动势，并且，这个P-N+硅片的空间电荷区大部分位于P-区域，再借助水体形成回路，为半导体纳米线光电催化层2供电，降低在紫外光照射过程中，半导体纳米线光电催化层2中产生的光生电子和空穴的复合率，提高催化效率。可见，本发明之半导体光电催化器件无需另接电源，结构简单。
附图说明
图1是用于制作本发明之半导体光电催化器件的P-N+硅片结构示意图。图2是本发明之半导体光电催化器件结构示意图，该图同时作为摘要附图；该图还是本发明之半导体光电催化器件工作状态示意图。
具体实施方式
本发明之利用PN结自供电的半导体光电催化器件如图1、图2所示，在P-N+硅片的P-区分布若干栅条1，自P-区至N+区掺杂浓度由稀变浓。P-N+硅片厚600μm，栅条1以下的P-区厚度为50～120μm，如100μm，N+区厚度为130～250μm，如200μm，栅条1的高为300～350μm，如300μm，宽为110～120μm，如114μm，栅条1间距为180～190μm，如185μm。栅条1的顶面和侧面覆盖有半导体纳米线光电催化层2。所述半导体纳米线为TiO2、ZnO、WO3、CdS或者ZnS纳米线；所述半导体纳米线光电催化层2的厚度为1～2μm。栅条1之间的P-区表面有一层SiO2膜层3，以利于紫外光入射P-N+结。
以TiO2为例，通过对本发明之利用PN结自供电的半导体光电催化器件的制作过程的说明，进一步说明其结构特征。在P-N+硅片的P-区一侧刻蚀一组栅条1。将该组栅条1浸泡在钛酸四丁酯的异丙醇溶液和无水乙醇中，在栅条1的顶面和侧面生成Si-Ti(OH)4，经退火处理后转变为Si-TiO2，此时在栅条1的顶面和侧面形成具有锐钛矿结构的TiO2籽晶层。将此时的该组栅条置于钛酸四丁酯、盐酸和水的混合液中，经过结晶生长过程，在栅条1的顶面和侧面形成一层TiO2纳米线，这就是所述半导体纳米线光电催化层2。在上述过程中不可避免会在栅条1之间的P-区表面也形成一层TiO2纳米线，于是采用等离子干法刻蚀将该层TiO2纳米线去除。最后经过稀硫酸浸泡，在栅条1之间的P-区表面生成SiO2膜层3。
Claims (4)
1.一种利用PN结自供电的半导体光电催化器件，其特征在于，在P-N+硅片的P-区分布若干栅条(1)，自P-区至N+区掺杂浓度由稀变浓，栅条(1)以下的P-区厚度为50～120μm；栅条(1)的顶面和侧面覆盖有半导体纳米线光电催化层(2)。
2.根据权利要求1所述的利用PN结自供电的半导体光电催化器件，其特征在于，N+区厚度为130～250μm，栅条(1)的高为300～350μm，宽为110～120μm，栅条(1)间距为180～190μm。
3.根据权利要求1所述的利用PN结自供电的半导体光电催化器件，其特征在于，所述半导体纳米线为TiO2、ZnO、WO3、CdS或者ZnS纳米线；所述半导体纳米线光电催化层(2)的厚度为1～2μm。
4.根据权利要求1所述的利用PN结自供电的半导体光电催化器件，其特征在于，栅条(1)之间的P-区表面有一层SiO2膜层(3)。
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