CN113481598B - 一种Zn-P-As晶体材料及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种Zn‑P‑As晶体材料及其制备方法和应用，所述Zn‑P‑As晶体材料中Zn、P、As的原子比为3：5：2.6，正交晶系，空间群为Cmcm，晶胞参数为
α＝β＝γ＝90°，保护性气氛或真空环境下，将单质As、单质P以及单质Zn球磨混合，升温至620℃～820℃下保温反应不低于6h即得。本发明所载的Zn‑P‑As晶体材料，其光学带隙约为1.2eV，与单晶Si(Eg:1.1～1.3eV)的带隙接近，作为半导体材料，在新型电子器件领域以及光伏领域具有潜在的应用前景。
Description
技术领域
本发明属于冶金技术及材料科学与工程技术领域，涉及一种新型半导体Zn-P-As晶体材料及其制备方法和应用。
背景技术
金属砷作为有色冶炼工业产出的副产品，全球年产量约为3万吨(以金属砷计)，其在地幔中丰度处于47位，并不是一种丰富的矿产资源。由于其化合物的独特性能，如GaAs具有高载流子迁移率而应用于高速响应计算元器件和高频发射电子器件上，InAs具有优异的光电性能用来制作光电二极管，BAs具有超高热导率而有望成为新一代超高速计算电子器件的备选晶体、Cd3As2为一种新型的量子霍尔效应weyl半导体，CrAs具有压力诱导的超导性能等等，使得砷化物应用成为一种探索新型应用功能材料的重要途径。
本方法开发设计了一种新型半导体晶体材料，与单晶Si(Eg:1.1～1.3eV)的带隙接近，其可能在新型电子器件以及光伏领域具有潜在的应用前景。
发明内容
本发明提供了一种新型半导体Zn-P-As晶体材料，其光学带隙约为1.2eV，与单晶Si(Eg:1.1～1.3eV)的带隙接近，在新型电子器件以及光伏领域具有潜在的应用前景。
本发明采用如下技术方案：
一种Zn-P-As晶体材料，Zn、P、As的原子比为3：5：2.6，正交晶系，空间群为Cmcm，晶胞参数为
α＝β＝γ＝90°。
本发明还提供了上述Zn-P-As晶体材料的制备方法，保护性气氛或真空环境下，将单质As、单质P以及单质Zn球磨混合，升温至620℃～820℃下保温反应不低于6h即得。
作为优选，所述保护性气氛为氩气或氦气气氛。
作为优选，所述单质As、单质P以及单质Zn的摩尔比为3：(4.8～5.1)：(2.5～2.7)；进一步优选为3：5：2.6。
作为优选，球磨混合后于30～40MPa压力下进行压片处理。
作为优选，升温速率不高于20℃/h；进一步优选为不高于10℃/h。本发明通过控制升温速率以确保固相反应充分，减少局部高温时气相挥发。
作为优选，保温反应不低于24h。
作为优选，保温反应后冷却，冷却过程中，以产物放置处为中心，维持中心比距中心5cm以外区域高30℃以上的温度差降至室温即可；进一步优选为温度差不低于50℃。本发明通过控制降温温度差使材料局部未参与反应残余原料挥发，确保整体上材料均匀、高纯。
本发明还提供了上述Zn-P-As晶体材料的应用，将其作为半导体，用于电子器件或光伏技术领域。
本发明通过将单质Zn、单质P和单质As球磨混合均匀，于620℃～820℃下进行充分反应结晶，高温保温去除可能的杂质，降温形成温度差确保可挥发杂质脱除，从而获得新型晶体结构的Zn-P-As晶体材料。
本发明的新型晶体结构的Zn-P-As晶体材料，为一种全新的半导体晶体材料，其结构信息通过单晶X射线衍射解析见图1，光学带隙见图4，约为1.2eV，与单晶Si(Eg:1.1～1.3eV)的带隙接近。
附图说明
图1为本发明实施例3的Zn-P-As晶体材料的晶体结构解析信息；
图2为本发明实施例3的Zn-P-As晶体材料的光学照片(a)和晶体结构(b)；
图3为本发明实施例1-3的产物的物相鉴定数据图；图中杂质主要为金属As(箭头标出所在峰位置)，实施例1-3均可获得新型晶体，其中实施例3获得晶体基本无杂质。
图4为本发明实施例3的Zn-P-As晶体材料的光学带隙测试图；晶体材料的光学带隙约为1.2eV。
具体实施方式
为阐述本发明的特征，结合实施例对本发明进行说明，本发明实施例均采用高纯石英管为容器，内径16mm，壁厚1.5mm，熔封后反应腔体长度约15cm，并在氩气保护的手套箱内(常压，含水率<1ppm，氧含量<1ppm)进行取样和配料准备，最后采用氢氧焰进行熔封。
实施例1
将1.745g单质Zn、1.330g单质P和1.320g单质As按照摩尔比Zn:P:As＝3:5:2进行配料，将物料研磨混匀后使用30～40MPa压力进行压片，装入石英管后经过进行真空熔封。之后，将石英管置于反应炉中，按照10℃/h升温速率升温至820℃，保温48h后，降温至620℃，维持反应产物区域620℃温度30min后自然降温，其他区域(距产物中心5cm以外区域)则直接自然降温至室温，控制反应产物区域与其他区域的温度差为50℃。取出样品，进行物相鉴定测试，结果见图3。
实施例2
将1.817g单质Zn、1.003g单质P和0.740g单质As按照摩尔比Zn:P:As＝3:9.5:6.5进行配料，将物料研磨混匀后使用30～40MPa压力进行压片，装入石英管后经过进行真空熔封。之后，将石英管置于反应炉中，按照10℃/h升温速率升温至820℃，保温48h后，降温至620℃，维持反应产物区域620℃温度30min后自然降温，其他区域(距产物中心5cm以外区域)则直接自然降温至室温，控制反应产物区域与其他区域的温度差为100℃。取出样品，进行物相鉴定测试，结果见图3。
实施例3
将1.077g单质Zn、0.851g单质P和1.071g单质As按照摩尔比Zn:P:As＝3:5:2.6进行配料，将物料研磨混匀后使用30～40MPa压力进行压片，装入石英管后经过进行真空熔封。之后，将石英管置于反应炉中，按照10℃/h升温速率升温至820℃，保温48h后，降温至620℃，维持反应产物区域620℃温度30min后自然降温，其他区域(距产物中心5cm以外区域)则直接自然降温至室温，控制反应产物区域与其他区域的温度差为50℃。取出样品，进行物相鉴定测试，结果见图3。
Claims (10)
1.一种Zn-P-As晶体材料，其特征在于：所述Zn-P-As晶体材料中Zn、P、As的原子比为3：5：2.6，正交晶系，空间群为Cmcm，晶胞参数为
α＝β＝γ＝90°。
2.权利要求1所述的Zn-P-As晶体材料的制备方法，其特征在于：保护性气氛或真空环境下，将单质As、单质P以及单质Zn球磨混合，升温至620℃～820℃下保温反应不低于6h即得。
3.根据权利要求2所述的制备方法，其特征在于：所述保护性气氛为氩气或氮气气氛。
4.根据权利要求2所述的制备方法，其特征在于：所述单质As、单质P以及单质Zn的摩尔比为3：(4.8～5.1)：(2.5～2.7)。
5.根据权利要求4所述的制备方法，其特征在于：所述单质As、单质P以及单质Zn的摩尔比为3：5：2.6。
6.根据权利要求2所述的制备方法，其特征在于：球磨混合后于30～40MPa压力下进行压片处理。
7.根据权利要求2所述的制备方法，其特征在于：升温速率不高于20℃/h。
8.根据权利要求2所述的制备方法，其特征在于：保温反应不低于24h。
9.根据权利要求2所述的制备方法，其特征在于：保温反应后冷却，冷却过程中，以产物放置处为中心，维持中心比距中心5cm以外区域高30℃以上的温度差降至室温即可。
10.权利要求1所述的Zn-P-As晶体材料或权利要求2-9任一项所述的制备方法制得的Zn-P-As晶体材料的应用，其特征在于：将其作为半导体，用于电子器件或光伏技术领域。
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| CN111455460A (zh) * | 2020-04-13 | 2020-07-28 | 中南大学 | 一种金属砷单晶的制备方法 |
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| CN111455460A (zh) * | 2020-04-13 | 2020-07-28 | 中南大学 | 一种金属砷单晶的制备方法 |
| CN112064116A (zh) * | 2020-09-14 | 2020-12-11 | 中国科学院上海硅酸盐研究所 | 一种制备InSeI单晶体的方法 |
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