CN111285396A - 一种Cu-In-Zn-S纳米球的制备方法及其在光响应探测器中的应用 - Google Patents
一种Cu-In-Zn-S纳米球的制备方法及其在光响应探测器中的应用 Download PDFInfo
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Abstract
本发明涉及一种Cu‑In‑Zn‑S纳米球的制备方法及其在光响应探测器中的应用。该纳米球由水热法一步反应制备，具有结晶性高，尺寸均匀，分散性好，带隙窄的优点，在可见光光谱范围具有良好的响应能力。将该纳米球分散于乙醇溶液中，通过喷涂或旋涂制备的光响应器件具有较高光电响应开关比，较快响应速度等优点。该纳米球在光响应器件中有着广阔的应用前景。
Description
技术领域
本发明涉及一种Cu-In-Zn-S纳米球的制备方法及其光响应探测器中的应用，属于纳米材料技术领域。
背景技术
光探测器是一种能够将光信号转变为电信号的光电器件，在通信、医疗、热成像、环境监测和国防科技领域都具有广泛的应用。其中高性能光探测器需要高灵敏和快速响应等性能。目前工业中使用的光响应器件主要是基于硅、氮化镓、铟镓砷等材料。其存在工作电压高、制备工艺复杂、成本高或毒性大等不足。
Cu-In-Zn-S(铜铟锌硫)是一种直接带隙半导体材料，具有带隙窄，毒性低，光吸收系数高等优点。尤其是将其制成纳米材料，具有优异的光学性能，在发光二极管、光催化、太阳能电池等方面具有广阔的应用前景。虽然在这些领域中可以说明Cu-In-Zn-S具有光电性质，但并非具有光电性质的材料均能作为探测材料应用于光响应器件中，不同的应用领域，对性能指标的要求也是不同的。在光响应器件中需要满足较好的灵敏度、响应速率、还有开关比等要求。目前尚未见到Cu-In-Zn-S四元合金纳米材料用于光响应探测器领域的公开报道。
铜、锌、硫元素在地壳中含量丰富。而随着回收提纯技术的不断提高，铟的供应业相对稳定。因此基于铜、铟、锌、硫的四元半导体纳米材料成本较低，具有潜在实用价值。因此，开发基于Cu-In-Zn-S纳米球的半导体光电器件对于低成本、高效率的光探测器具有重要意义。
发明内容
为了解决背景技术中的技术问题，本发明的目的在于：(1)提供一种Cu-In-Zn-S纳米球的制备方法；(2)提供一种Cu-In-Zn-S纳米球在构造光响应器件中的应用。该光响应器件具有易制备、低成本、响应迅速等优点。
为达到上述发明目的，本发明提供如下技术方案：
a、Cu-In-Zn-S纳米球的反应溶液的配制：将氯化亚铜、氯化铟、二水乙酸锌、硫代乙酰胺充分溶解于去离子水中，得混合水溶液。
进一步的，步骤a中氯化亚铜与氯化铟的摩尔比为9:1至1:9。
优选为氯化亚铜与氯化铟的摩尔比为1：9。
进一步的，硫代乙酰胺在水溶液中的浓度为0.17mol/L，二水乙酸锌在水溶液中的浓度为0.07mol/L。
b、Cu-In-Zn-S纳米球的制备：将步骤a中配置好的溶液转移至反应釜中密封，加热反应后固液分离得到固相。将固相经清洗、干燥后制得Cu-In-Zn-S纳米球粉体。
进一步的，步骤b中，所述加热反应温度可以为150-200℃。
进一步的，步骤b中，所述加热反应时间可以为10-20小时。
进一步的，步骤b中，所述固液分离为以6000转/分钟离心5分钟后收集下层固体。
进一步的，步骤b中，所述清洗为使用功率为180瓦的超声清洗机清洗3遍，每遍10分钟。
进一步的，步骤b中，所述干燥为60℃下干燥10h。
上述方法制得的Cu-In-Zn-S纳米球平均直径为150-200纳米，是由许多纳米晶聚集生长成球得到多晶纳米球，Cu-In-Zn-S的晶相为立方相。且相比于已有文献报道的在常温下制备的Cu-In-Zn-S纳米球(对比例3)，本发明制得的Cu-In-Zn-S纳米球，结晶峰相较窄，信号较强，结晶性得到明显改善，将其用于光响应器件中，能取得优异的光响应效果。
2、由所述的方法制备Cu-In-Zn-S纳米球应用于光响应探测器。
光响应探测器的制备方法为：
a、制备的Cu-In-Zn-S纳米球分散于乙醇溶液形成悬浊液；
b.以叉指电极为基底，将步骤a中制备的悬浊液均匀喷涂在叉指电极表面，然后在80℃进行干燥，从而在叉指电极表面形成一层Cu-In-Zn-S纳米球薄膜，即构造出Cu-In-Zn-S光响应探测器。
进一步的，步骤a中，所述悬浊液浓度可以为5～10mg/mL；
进一步的，步骤b中，喷涂时间可以为60～120秒；
进一步的，为可见光范围响应的光响应探测器。
本发明的有益效果在于：本发明提供一种Cu-In-Zn-S纳米球的制备方法，该方法制得Cu-In-Zn-S能作为光探测材料用于光响应探测器中。不仅原料来源丰富，而工艺简单易行，适用于工业化生产。通过控制反应前驱物比例，制备了不同成分的Cu-In-Zn-S纳米球。将该纳米球应用于光响应器件，光源照射条件下Cu-In-Zn-S纳米球受到光子激发，内部会产生电子-空穴对，从而产生光生载流子。当对器件施加偏置电压则产生光电流，导致电流增加。当移除光源后，不在产生光生载流子，光电流消失，回路中的电流值迅速下降。且由成分为Cu0.03In0.17Zn0.81S的纳米球构造的光响应器件具有良好的响应特性(响应时间约为0.04秒)，光电流与暗电流之比(开关比)达到3.2，具有广阔的应用前景，为设计新型光响应器件提供了新的思路。
附图说明
图1是实施例1中制备的Cu-In-Zn-S纳米球的扫描电镜照片。
图2是实施例1和对比例1-2中制备的三种Cu-In-Zn-S(组分分别为Cu0.07In0.01Zn0.61S,Cu0.08In0.07Zn0.72S和Cu0.03In0.17Zn0.81S)纳米球的X射线衍射图。
图3是实施例1和对比例1-2中制备的三种Cu-In-Zn-S纳米球的吸收光谱和分散于水溶液中的照片。
图4是实施例1中制备的基于Cu0.03In0.17Zn0.81S纳米球的光响应器件的时间-电流曲线图。偏转电压分别为1-5V。激发波长分别为405nm和600nm，激发功率为20mW。
图5是实施例1中制备的基于Cu0.03In0.17Zn0.81S纳米球的器件在周期性光照信号下时间-电流曲线中的一个周期的放大图。
图6是对比例1中制备的基于Cu0.08In0.07Zn0.72S纳米球的器件在周期性光照信号下时间-电流曲线中的一个周期的放大图。
图7是对比例2中制备的基于Cu0.07In0.01Zn0.61S纳米球的器件在周期性光照信号下时间-电流曲线中的一个周期的放大图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
制备Cu0.03In0.17Zn0.81S纳米球
a.称取131.7mg四水合三氯化铟，4.8mg氯化亚铜，438mg二水乙酸锌，400mg硫代乙酰胺，加入去离子水30mL充分溶解。
b.将步骤a中的溶液转移至50mL聚四氟乙烯反应釜中密封，在180℃下反应15小时后，自然冷却至室温。
c.将步骤b中得到的溶液以5000转/分钟的速度离心5分钟，取下层固体。将固体在功率为180瓦的超声波清洗机中用去离子水清洗3遍。最后在60℃烘箱中干燥10小时得到Cu0.03In0.17Zn0.81S纳米球粉体。
对比例1
对比例1与实施例1相比，区别在于：原料加入量不同，分别称取73.3mg四水合三氯化铟，24.7mg氯化亚铜，438mg二水乙酸锌，400mg硫代乙酰胺，去离子水30mL充分溶解。其余制备方法相同，得到Cu0.08In0.07Zn0.72S纳米球粉体。
对比例2
对比例2与实施例1相比，区别在于：原料加入量不同，分别称取14.6mg四水合三氯化铟，44.6mg氯化亚铜，438mg二水乙酸锌，400mg硫代乙酰胺，去离子水30mL充分溶解。其余制备方法相同，得到Cu0.07In0.01Zn0.61S纳米球粉体。
对比例3
对比例3与实施例1相比于，原料加入量相同，区别在于：将步骤b中在180℃下反应替换成在室温下反应，其余操作与实施例1相同，得到Cu-In-Zn-S纳米球粉体。
在室温下搅拌反应得到CuInZnS纳米球粉体，结晶峰很宽，信号强度低，结晶性较差，会对光响应效果产生不利影响，无法达到实施例1的响应效果。
利用扫描电镜、X射线衍射仪、紫外-可见分光光度计对实施例与对比例中制备的粉体进行表征。结果如图1至图3所示。由图1可知，所制备的Cu-In-Zn-S纳米球直径约为200纳米，形貌尺寸均一。由图2可知，当Cu/In摩尔比为9:1时，对比例2所得产物为六方CuS相(JCPDS#65-3588)与立方ZnS相(JCPDS#65-0309)的混合物，当In含量增加，对比例1中主要为立方ZnS相，但也存在少量六方CuS相。而Cu/In摩尔比为1:9时，实施例1中制得的产物为较纯的ZnS闪锌矿结构。由SEM照片的表面粗糙度及XRD衍射峰较宽的半峰宽可知，实施例与对比例中的Cu-In-Zn-S纳米球是由许多纳米晶粒组成。由图3可知，不同组分制备的Cu-In-Zn-S纳米球在可见光光谱范围均有吸收能力，但吸收强度有所不同，其乙醇溶液呈现不同的颜色。
实施例2
Cu-In-Zn-S纳米球在构造光响应器件中的应用
a.将实施例与对比例中制备的Cu-In-Zn-S纳米球分别分散于乙醇溶液形成悬浊液，浓度为5mg/mL。
b.以叉指电极为基底，将步骤a中制备的悬浊液均匀喷涂在叉指电极表面，喷涂60秒，然后在80℃进行干燥，从而在叉指电极表面形成一层Cu-In-Zn-S纳米球薄膜(对厚度无要求)，即构造出完整的Cu-In-Zn-S光响应器件。
c.使用Keithley 4200，在激光器照射下(波长分别为405和600纳米，功率为20mW)测试光响应器件性能，测试结果如图4-7所示。
图4是基于Cu0.03In0.17Zn0.81S的光响应器件的时间-电流曲线图。偏转电压分别为1-5V，激发光波长分别为405nm和600nm。由图4可知，在5V偏压条件下，器件的开关比(光电流与暗电流之比)为3.2，显示出较好光电响应特性。图5是上述器件在周期性光照信号下时间-电流曲线中的一个周期的放大图。由图可知，器件的光响应速度迅速，上升时间与下降时间均为0.04s(λ＝405nm)和0.07s/0.09s(λ＝600nm)。图6是基于Cu0.08In0.07Zn0.72S的光响应器件的光照条件下时间-电流曲线中的一个周期，响应时间为2.24s/4.62s(λ＝405nm)。图7是基于Cu0.07In0.01Zn0.61S的光响应器件的光照条件下时间-电流曲线中的一个周期，响应时间为3.02s/6.83s(λ＝405nm)。
通过实施例1与对比例1-2在结构与性能中的对比可知，较高的Cu/In比例下产物为两相共存，由于晶格匹配度较低，易产生较多缺陷，影响光电性能。而较低的Cu/In比例下，产物为较纯的ZnS立方相，所制备的光响应器件也表现出较好的光响应特性。通过实施例1制备的Cu-In-Zn-S可以构造一个具有良好光响应性能的器件。
实施例中未注明具体条件者，按照常规条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (9)
1.一种Cu-In-Zn-S纳米球的制备方法，其特征在于，步骤如下：
步骤1：配制氯化亚铜，氯化铟，二水乙酸锌和硫代乙酰胺的混合水溶液；
步骤2：将配制好的溶液转移至反应釜中密封，加热反应后自然冷却至室温；
步骤3：离心步骤2的反应溶液，得到固相后清洗、干燥，得到Cu-In-Zn-S纳米球粉体。
2.如权利要求1所述Cu-In-Zn-S纳米球的制备方法，其特征在于：所述氯化亚铜与氯化铟的摩尔比为1：9～9：1。
3.如权利要求2所述Cu-In-Zn-S纳米球的制备方法，其特征在于：所述氯化亚铜与氯化铟的摩尔比为1:9。
4.如权利要求1所述Cu-In-Zn-S纳米球的制备方法，其特征在于：所述硫代乙酰胺在混合水溶液中的浓度为0.17mol/L，二水乙酸锌在混合水溶液中的浓度为0.07mol/L。
5.如权利要求1所述Cu-In-Zn-S纳米球的制备方法，其特征在于：步骤2中，所述加热反应温度为150-200℃，加热反应时间为10-20小时。
6.如权利要求1所述Cu-In-Zn-S纳米球的制备方法，其特征在于：步骤2中，所述Cu-In-Zn-S的晶相为立方相，Cu-In-Zn-S纳米球平均直径为150-200纳米。
7.如权利要求1-6任一项所制备的Cu-In-Zn-S纳米球作为光探测材料在光响应探测器中的应用。
8.如权利要求7所述Cu-In-Zn-S纳米球作为光探测材料在光响应探测器中的应用，其特征在于：
将Cu-In-Zn-S纳米球粉体分散于乙醇制成悬浊液，然后将悬浊液喷涂于叉指电极表面，干燥成膜，构造得到光响应探测器。
9.如权利要求8所述Cu-In-Zn-S纳米球作为光探测材料在光响应探测器中的应用，其特征在于：为可见光范围响应的光响应探测器。
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