CN117080283A - 一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计 - Google Patents
一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计 Download PDFInfo
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
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- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
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Abstract
本发明公开了一种基于铜镉锌锡硒(Cu2Cd(1‑x)ZnxSnSe4，以下简称CCZTSe)光电吸收层的宽波段的光电型激光功率计及其制备方法，克服了现有的光电型激光功率计在宽波段外量子效率低的困难，填补了我国自主生产的光电型激光功率计的空白。主要依次包括光电转换单元：硅基衬底、电极层、P型半导体层、光吸收层、n型半导体层、缓冲层、窗口层、N i‑A l‑N i电极层。信号处理单元、A/D转换器单元、激光显示单元。所述激光功率计探头还设置了连续型衰减片位于探头前方。本发明既具有测量波长范围宽，响应速度快，还具有噪声小，稳定性好的优点。
Description
技术领域
本发明涉及光电二极管型激光功率测量技术
背景技术
激光器于1960年被梅曼发明出来后，经过革新，逐渐应用在光纤通讯、汽车雷达、激光加工、军事国防等重要领域，对激光各个参数的检测也是必不可少的一部分，目前占市场主体部分的激光功率就是光电型和热电型，国内光电型激光功率计80％以上的市场被国外厂商垄断。光电型激光功率计可用于现代光纤通讯等小功率光测量，测量准确，误差小，精度高，响应速度快，但是测量波长范围小，易受到噪声干扰，主要用于小功率测量。而热电型激光功率计测量波长宽，测量功率大，但是测量精度不高。
激光最重要的参数便是功率和波长，而激光功率计的设计既要满足对入射激光波长的测量，还要保证在一定的激光强度下不会损伤光电转换探头。目前市场上的光电型激光功率计探头材料有Si、Pb、InGaAs等，检测波长有限，并且InGaAs材料本身比较昂贵，难以在工业中大批量生产，待研发一些波段更宽、效率更高、精度也要更高等综合性能较好的激光功率计。
光电二极管型激光功率计的测量原理是光照射在激光功率计的探头(P-N结)上，P-N结处的电子吸收能量，电子吸收的能量大于原子核对电子的束缚能量时，电子在人为反向电压的作用下通过导线传输形成电流，该电流分为光生电流和暗声电流，通过后期的电子电路的信号放大和模数转换等，再被LCD板接收到，通过测出电流的大小转换成对光功率的测量，入射激光光强度越高，电流越大，测出来的激光功率也越大。
发明内容
针对光电型激光功率计存在的可测波长范围窄的问题，本发明提供了一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，具有的优点是检测波长覆盖范围宽，测量精度高，响应时间短，可用于400-1700nm激光功率的测量。
一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，主要依次包括光电转换单元：硅基衬底、电极层、P型半导体层、光吸收层、n型半导体层、缓冲层、窗口层、Ni-Al-Ni电极层。信号处理单元、A/D转换器单元、激光显示单元。所述激光功率计探头还设置了连续型衰减片位于探头前方。
进一步地，所述光电转换单元是一由新材料CCZTSe制备而成的探头。
进一步地，所述探头的制作主要由以下6步完成：直流磁控溅射制备Mo接触电极、激光划线、共蒸发法制备P型层、CBD法制备N型层、直流磁控溅射制备窗口层、电子束蒸发法制备Ni-Al-Ni电极。
进一步地，所述探头表面涂覆了一层吸光涂层。
进一步地，所述探头表面涂覆了一层增透膜。
进一步地，所述激光功率计探头前方设置了一个衰减片。
进一步地，所述激光功率计探头与信号处理单元连接，该单元用于对来自光电转换的电信号进行放大、保持、电路积分、整流、滤波。。
进一步地，所述信号处理单元与A/D转换单元连接，A/D转换器采用的是逐次比较型，具有速度较快、功耗低的特点。
进一步地，所述A/D转换单元与光功率显示单元连接，光功率显示单元由LCD板和软件组成。
综上，本发明还具有结构简单，原材料成本比较低的优点。
附图说明
图1为本发明实施例中探头结构示意图
图2为本发明实施例中激光划线示意图
图3为本发明实施例中EQE测试折线图
图4四为本发明实施例中暗电流测试折线图
具体实施方式
为了更加清楚地说明本发明的目的、特征和技术方案，接下来将以结合附图的方式，对本发明再次做出更加详细的介绍。必须强调的是：下面描述的实施例仅仅是本发明实施例中的一部分，并不代表本发明全部实施例。基于本发明中的实施例，本发明的技术人员在未创造出创新性的劳动之前所获得的所有其他实施例，都属于本发明的保护范围。
本实施例提供了一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，该激光功率计最主要的核心部位是探头，探头吸收层最主要材料是Cu2CdxZn1-xSnSe4。
本实施例最主要的优点之一是可以探测350nm-1700nm宽光谱波段的激光，如图三所示，峰值效率可达到83％，400～1000nm的效率可达60％以上，优点之二是暗电流可达10-9数量级。
在本实施例中，激光功率计探头结构如图一所示，探头主要由硅基衬底、Mo接触电极、CCZTSe吸收层、CdS缓冲层、I-ZnO&A-ZnO窗口层、顶电极层。
在本实施例中，所采用的Si片是直拉法制备的P型单面抛光硅片。
在本实施例中，Mo接触电极的制备方法采用的是直流磁控溅射，Mo对角电阻为0.8～1Ω，台阶厚度800～815nm。
在本实施例中，共有俩次激光划线，第一次是在Mo接触电极上画38条横线，如图二(a)。光刻胶选用的是正性光刻胶，曝光激光波长是532nm，阵列列宽为2.54mm，共38条。先在匀胶机上旋涂是光刻胶铺开，前烘1分30秒，再在显影液中显影三十秒，用去离子水冲洗，用氮气吹干，然后放进Mo刻蚀液中刻饰30s去除划线部位的反应物，用去离子水冲洗，N2吹干，显微镜观察表面刻饰情况，最后用丙酮除去剩余的光刻胶，再用去离子水冲洗吹干。
在本实施例中，吸收层的制备方法是共蒸发镀膜。
共蒸发的步骤是先在软件上设置好温度，再打开Cu、Cd、Zn、Sn、Se五种元素的挡板，再打开样品的挡板，再使得NaF蒸发。
在本实施例中，制备硫化镉的方法是CBD法，生长最好的时间是9分钟。
制备硫化镉的步骤是：先称取5.694g硫脲溶于150ml的去离子水中，磁力搅拌15分钟。再称取0.184g硫酸镉溶于60ml去离子水中，再称取45ml的氨水溶于其中，磁力搅拌15分钟。将Si片固定于反应容器中，且镀膜面向下。将反应物硫脲和硫酸镉溶液倒入反应器皿中，量取425ml去离子水对盛反应物的烧杯清洗后加入反应器皿中。加热计时九分钟直到反应结束。
在本实施例中，窗口层的制备方法是直流磁控溅射法。
I-ZnO是本征氧化锌，A-ZnO是掺杂铝元素的氧化锌。
I-ZnO需要先镀四层疏松层，再镀26层致密层。
在本实施例中，共有俩次激光划线，第二次是在A-ZnO上划38条竖线，如图二(b)所示。光刻胶选用的是正性光刻胶，曝光激光波长是532nm，阵列列宽为2.54mm，共38条。先在匀胶机上旋涂是光刻胶铺开，前烘1分30秒，再在显影液中显影三十秒，用去离子水冲洗，用氮气吹干，然后放进Mo刻蚀液中刻饰30s去除划线部位的反应物，用去离子水冲洗，N2吹干，显微镜观察表面刻饰情况，最后用丙酮除去剩余的光刻胶，再用去离子水冲洗吹干。
在本实施例中，顶电极的制备方法采用的是电子束蒸发法。
在本实施例中，由于测量的波长是350nm～1700nm的波长，因此在不同波长范围，有对应的衰减片对激光进行衰减，衰减范围按照激光波长的增加而增大，损伤阈值也逐渐变高。
在本实施例中，光电转换单元连接着信号处理单元，信号处理单元包括小信号放大器，对来自光电探头的微弱电信号几百mV或者几百μv的电压转换成A/D转换单元能够处理的0-5v的电压值。
在本实施例中，信号处理单元连接着A/D转换单元，A/D转换器采用的是逐次比较型，具有速度较快、功耗低的特点。
在本实施例中，A/D转换单元连接着功率显示单元，光功率显示单元LCD板和软件组成，对来自数模转换的数字信号进行显示，并对其进行电信号积分复位，进行下一次测量。
以上对本发明进行了详细、客观的阐述，目的就是为了方便理解本发明。此外必须强调的是：除了以上阐述的本实施例以外，本发明还可以采用其他方式来实施。本领域相关技术人员可以对以上所描述的技术方案进行改动，或者对其中所描述的本发明的特征进行改动。
因此本发明，不受上面公开的具体实施例的限制。
Claims (14)
1.一种基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征包括：
光电转换单元，它是由新型薄膜材料铜镉锌锡硒组成的探头，用于吸收激光，并把光信号转换为电信号。
衰减片单元，用于对激光进行衰减，增加所测量激光功率的量程。
信号处理单元，用于对来自光电转换的电信号进行放大、保持、电路积分、整流、滤波。
A/D转换器单元，用于实现对放大器增益控制、A/D转换
激光显示单元，用于读数、设置量程、复位。
2.如权利要求1所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征包括：光电转换单元核心是探头，探头主要由硅基衬底、Mo接触电极、P型半导体层、光吸收层、n型半导体层、缓冲层、窗口层、顶电极层。用于吸收激光。探头制备过程如下：
Step1采用直流磁控溅射在Si片上镀Mo接触电极。
Step2将第一步中样品进行光刻。光刻胶选取正性胶，旋涂、前烘后再进行曝光、显影、刻蚀，最后清洗干净表面的光刻胶。
Step3将第二步中的样品利用共蒸发法生长出CCZTSe薄膜吸收层材料，并掺入NaF。
Step4将第三步的样品用化学水浴法生长出CdS薄膜。
Step5将第五步的样品利用磁控溅射的方法生长出窗口层i-ZnO和导电层a-ZnO。
Step6将第六步的样品利用电子束蒸发法生长出Ni-Al-Ni电极。
Step7再对第七步的样品进行第二次光刻。
3.如权利要求2中Step1所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，所采用的Si片是用直拉法制备的P型单面抛光硅片，所采用的Mo接触电极是利用直流磁控溅射设备镀的几层疏密程度不同的薄膜，分别是疏松-致密-致密-致密-致密-疏松。
4.如权利要求2中Step2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，光刻胶选用的是正性光刻胶，曝光激光波长是532nm，阵列列宽为2.54mm，共38条。先在匀胶机上旋涂是光刻胶铺开，再在显影液中显影三十秒，用去离子水冲洗，用氮气吹干，然后放进Mo刻蚀液中刻饰30s去除划线部位的反应物，用去离子水冲洗，N2吹干，显微镜观察表面刻饰情况，最后用丙酮除去剩余的光刻胶，再用去离子水冲洗吹干。
5.如权利要求2中Step3所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，所采用的CCZTSe薄膜的制备方法是物理气相沉法中的共蒸发法，Cu、Zn、Sn、Se、Cd五种元素同时蒸发，到达样品表面。NaF采用的是高温非共生掺杂的方法进行掺杂。
6.如权利要求2中Step4所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，所采用的方法是化学水浴法，先称量5.694g硫脲于烧杯A中，加入150ml去离子水，搅拌10分钟，再称量0.184g硫酸镉于烧杯B中，加入60ml去离子水，搅拌10分钟，再向硫酸镉溶液中加入45ml氨水，继续搅拌5分钟。水浴加热锅加热至67℃，将样品镀膜面朝下固定在反应容器中，依次加入硫酸镉溶液、硫脲溶液，425ml去离子水，将反应器皿放入水浴锅中加热9分30秒，利用硫脲、硫酸镉和氨水参与反应生成CdS，再在180℃烘箱中烘烤1分30秒。
7.如权利要求2中Step5所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，所采用的溅射方法是直流磁控溅射，先在CdS表面溅射一层i-ZnO，再在表面溅射一层A-ZnO，作为窗口层。
8.如权利要求2中Step6所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，所镀电极是先镀一层Ni，再镀一层Al，最后镀一层Ni。
9.如权利要求2中Step7所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于，与第一次光刻不同的是阵列划分均垂直于第一次的激光划线。
10.如权利要求2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于：所述的衰减片位于探头上方。
11.如权利要求2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于：所述的信号处理单元包括小信号放大器，对来自光电探头的微弱电信号几百mV或者几百μv的电压转换成A/D转换单元能够处理的0-5v的电压值。
12.如权利要求2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于：所述的信号处理单元还包括对信号最大值的维持。直到积分复位后，开始下一次激光信号的放大和维持。
13.如权利要求2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于：A/D转换器采用的是逐次比较型，具有速度较快、功耗低的特点。
14.如权利要求2所述的基于新材料薄膜铜镉锌锡硒光吸收层的宽波段的光电型激光功率计，其特征在于：光功率显示单元LCD板和软件组成，对来自数模转换的数字信号进行显示，并对其进行电信号积分复位，进行下一次测量。
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