WO2021189874A1 - 一种SiP晶体生长调控方法 - Google Patents

一种SiP晶体生长调控方法 Download PDF

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WO2021189874A1
WO2021189874A1 PCT/CN2020/129202 CN2020129202W WO2021189874A1 WO 2021189874 A1 WO2021189874 A1 WO 2021189874A1 CN 2020129202 W CN2020129202 W CN 2020129202W WO 2021189874 A1 WO2021189874 A1 WO 2021189874A1
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sip
preparing
crystal
phosphorus
crystals
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喻学锋
喻彬璐
王佳宏
杨娜
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/005—Growth of whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles

Definitions

  • the invention relates to the growth regulation and control of single crystal materials, in particular to a regulation and control method for the growth of large-size and high-crystallinity SiP crystals.
  • SiP As a P-type direct band gap semiconductor, SiP is already a "star" material in the field of optical communications, and is considered a semiconductor material with great potential for the development of silicon photonics technology.
  • the band gap of bulk SiP is 1.69 eV.
  • the orthogonal crystal structure of SiP often results in a two-dimensional layered structure, and the band gap width of SiP will increase as the layered structure becomes thinner. It is reported in the literature that a single-layer thickness of nano-SiP is expected to be used for blue LED light emission. Shandong University uses a high-temperature melting method to prepare SiP single crystals and use them to make optoelectronic devices.
  • Single crystal materials are popular because of their high crystallinity, good orientation and stable structure.
  • the chemical vapor transport method is an effective and universal method for preparing single crystal materials.
  • the preparation of single crystals by purely using raw materials and transport agents often requires a long time and high reaction temperature, and this often only yields small-sized single crystals.
  • the reaction energy barrier can be effectively reduced, and large-size single crystals can be obtained.
  • the purpose of the present invention is to provide a method for effectively regulating the growth of SiP crystals by using a chemical vapor transport method, and adding a suitable regulating agent to obtain a centimeter-level size and high crystallinity SiP linear crystal.
  • the method for preparing a SiP crystal material provided by the present invention includes the following:
  • the quartz tube is vacuum-sealed and sintered at a high temperature in a heating device for a certain period of time;
  • the amount ratio of Si in the silicon source: P in the phosphorus source: transport agent: regulator in step (1) is 1:1: (0.005-0.5): (0.01-0.1);
  • the silicon source includes one or a combination of crystalline silicon, amorphous silicon, and silicon tetraiodide;
  • the phosphorus source includes one or a combination of crystalline phosphorus, amorphous phosphorus, and phosphorus triiodide;
  • the transport agent is iodine elementary substance and iodide, characterized in that the iodide is solid, including metal iodide and non-metal iodide;
  • the control agent includes one or a combination of elemental sulfur, elemental selenium, and elemental tellurium.
  • the heating equipment mentioned in step (2) is one of a single temperature zone tube furnace, a multi-temperature zone tube furnace (dual temperature zone and above) muffle furnace, a box furnace, a microwave oven or a single crystal furnace;
  • the calcination conditions are as follows: the temperature is set at 900-1200°C, and the sintering time is 12-680h;
  • the solvents mentioned in step (3) are acetone and ethanol respectively.
  • the present invention has the following beneficial effects:
  • the SiP crystal growth preparation method provided by the present invention has a simple and mature process, a wide range of raw materials sources and is cheap, and a high yield.
  • Figure 1 shows the XRD (a) and Raman spectrum (b) of the SiP crystal in Example 1 of the present invention.
  • FIG. 2 shows the SEM (a) and SEM Mapping (b) of the SiP crystal in Example 1 of the present invention.
  • amorphous silicon powder 2.06g of phosphorus triiodide, 14.8mg of bismuth triiodide, 2mg of sulfur and 16mg of tellurium powder in the glove box.
  • the sealed quartz tube is placed in a single crystal furnace with a sintering temperature of 950°C and a reaction time of 96h. After the furnace body is cooled down, SiP linear crystals are obtained, which are cleaned with acetone and ethanol, and vacuum dried.
  • amorphous silicon powder 2.06g of phosphorus triiodide, 14.8mg of bismuth triiodide, 2mg of sulfur and 16mg of tellurium powder in the glove box. Grind and mix the raw materials evenly, and add them to a quartz tube with a length of 15cm and an inner diameter of 26mm. , After vacuuming, seal the quartz tube with a hydrogen oxygen machine. The sealed quartz tube was placed in a single crystal furnace, the sintering temperature was 950°C, and the reaction time was 96h. After the furnace body was cooled down, the SiP linear crystals could not be obtained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

本发明公开一种一磷化硅(SiP)晶体生长调控方法，该方法涉及单晶材料生长。制备方法是将硅源、磷源、输运剂、调控剂一起真空密封于石英管中，经过高温烧结成功得到SiP线状单晶，晶体长度可达到厘米级。该方法通过引入合适的调控剂便能改变SiP晶体形貌，晶体尺寸显著增大，并且大大提高晶体结晶性，这对于获得高质量单晶SiP具有重要意义。

Description

一种SiP晶体生长调控方法 技术领域
本发明涉单晶材料的生长调控，具体涉及一种大尺寸、高结晶性的SiP晶体生长的调控方法。
 背景技术
SiP作为一种P型直接带隙半导体，在光通讯领域已经是一种“明星”材料，被认为是发展硅光子技术极具潜力的半导体材料。块体SiP的带隙在1.69eV，同时，SiP的正交晶体结构往往得到二维层状结构，SiP的带隙宽度会随着层状结构的减薄而增大。文献报道单层厚度的纳米SiP有望用于蓝色LED发光，山东大学利用高温熔融法制备出SiP单晶并用于制作光电器件。
单晶材料具有结晶性高、取向性好、结构稳定的特点而倍受青睐。化学气相输运法是一种有效且通用制备单晶材料的方法，单纯利用原料和输运剂制备单晶往往需要长时间和高的反应温度，而这也往往只能得到小尺寸单晶。通过引入调控剂可以有效降低反应能垒，并且能得到大尺寸单晶。
 技术问题
本发明的目的是，提供一种利用化学气相输运法有效调控SiP晶体生长的方法，加入合适的调控剂获得厘米级尺寸、高结晶性的SiP线状晶体。
 技术解决方案
本发明提供的一种SiP晶体材料的制备方法包括如下：
（1）在手套箱中称取一定比例的硅源、磷源、输运剂、调控剂，充分混合均匀转移至石英管中；
（2）抽真空密封石英管，在加热装置中高温烧结一定时长；
（3）冷却后用溶剂进行清洗，真空干燥后得到材料。
上述步骤中，步骤（1）中硅源中Si：磷源中P：输运剂:调控剂的物质的量比为1：1：(0.005-0.5)：(0.01-0.1)；
所述硅源包括结晶态硅、无定形硅、四碘化硅中的一种或几种的组合；
所述磷源包括晶态磷、无定形磷、三碘化磷中的一种或几种的组合；
所述的输运剂为碘单质及碘化物，其特征在于，碘化物为固态，包括金属碘化物和非金属碘化物；
所述调控剂包括单质硫、单质硒、单质碲中的一种或几种的组合。
步骤（2）中所述的加热设备为单温区管式炉、多温区管式炉(双温区及以上)马弗炉、箱式炉、微波炉或单晶炉中的一种；
所述的煅烧条件为，温度设定为900～1200℃，烧结时间为12～680h；
步骤（3）中所述的溶剂分别为丙酮、乙醇。
 有益效果
与现有技术相比，本发明具有以下有益效果：
（1）本发明提供的调控SiP晶体生长制备方法，未增加工艺复杂基础上通过简单的引入调控剂，在同一烧结条件下获得尺寸更大、结晶性更高、产率更高的SiP线状单晶。
（2）本发明提供的SiP晶体生长制备方法工艺简单成熟、原料来源广泛丰富且廉价，产量高。
 附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
图1为本发明实施例1中的SiP晶体XRD（a）和拉曼图谱（b）。
图2为本发明实施例1中的SiP晶体的SEM（a）和SEM Mapping（b）。
 本发明的实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所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。
下面结合具体实施例对本发明的应用原理作进一步描述。
实施例1
在手套箱中分别称取0.14g 无定形硅粉、0.16g无定形红磷粉、15.9mg四碘化碲、1.6mgS粉，原料进行充分研磨均匀，加入长11cm，内径为11mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于箱式炉中，炉温设置为1200℃，反应时间为12h，炉体降温后取出SiP线状晶体，并用丙酮、乙醇进行清洗，真空干燥，图1a的XRD和图1b的Raman结果表明得到的确实为SiP，并且XRD峰型尖锐且峰强很高，表明该晶体结晶性很高。图2a和图2b表明该物质Si和P的原子比为1:1，无其它杂质。
实施例2
在手套箱中分别称取0.28g结晶硅粒粉、0.31g结晶态磷、1.275 g碘单质、79mg单质硒，原料进行充分研磨均匀，加入长25cm，内径为16mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于马弗炉中，温度为900℃，反应时间为680h，炉体降温后取出SiP线状晶体，并用丙酮、乙醇进行清洗，真空干燥。
实施例3
在手套箱分别称取2.68g四碘化硅、0.16g无定形磷、7.3mg碘化氨、32mg碲粉，原料进行充分研磨均匀，加入长18cm，内径为18mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于双温区管式炉中，左端温度为1100℃，右端温度为1000℃，原料处于高温段，反应时间为350h，最后在低温段得到产物，并用丙酮、乙醇进行洗涤，抽真空干燥。
实施例4
在手套箱分别称取0.14g无定形硅粉、2.06g三碘化磷、14.8mg三碘化铋、2mg硫和16mg碲粉，原料进行研磨混合均匀，加入长15cm，内径为26mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于单晶炉中，烧结温度为950℃，反应时间为96h，炉体降温后得到SiP线状晶体，并用丙酮、乙醇进行清洗，抽真空干燥。
对比实施例1
在手套箱中分别称取0.14g无定形硅粉、0.16g无定形红磷粉、15.9mg四碘化碲，不加入调控剂，三者进行研磨混合均匀，加入长11cm，内径为11mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于箱式炉中，炉温设置为1200℃，反应时间为12h，冷却后石英管内并未发现SiP线状晶体。
对比实施例2
在手套箱中分别称取0.28g结晶硅粒粉、0.31g结晶态磷、1.275 g碘单质，原料进行充分研磨均匀，加入长25cm，内径为16mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于马弗炉中，温度为900℃，反应时间为680h，炉体降温后并未能得到SiP线状晶体。
对比实施例3
在手套箱分别称取2.68g四碘化硅、0.16g无定形磷、7.3mg碘化氨、32mg碲粉，原料进行充分研磨均匀，加入长18cm，内径为18mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于双温区管式炉中，左端温度为1100℃，右端温度为1000℃，原料处于高温段，反应时间为350h，炉体降温后在石英管内并未得到SiP线状晶体。
对比实施例4
在手套箱分别称取0.14g无定形硅粉、2.06g三碘化磷、14.8mg三碘化铋、2mg硫和16mg碲粉，原料进行研磨混合均匀，加入长15cm，内径为26mm的石英管内，抽真空后用氢氧机密封石英管。将封好的石英管置于单晶炉中，烧结温度为950℃，反应时间为96h，炉体降温后并未能得到SiP线状晶体。

Claims (9)

  1. 一种调控SiP晶体生长的方法，其特征在于，包括以下步骤：将硅源、磷源按照SiP化学计量比称量混匀，加入一定物质的量比例的输运剂和调控剂，进行抽真空密封于石英管中，在加热装置中高温烧结一定温度和时长得到SiP晶体。
  2. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述硅源中Si:磷源中P:输运剂:调控剂按照物质的量比为1 : 1：(0.005-0.5)：(0.01-0.1)称量混合。
  3. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述硅源包括结晶态硅、无定形硅、四碘化硅中的一种或几种的组合。
  4. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述磷源包括晶态磷、无定形磷、三碘化磷中的一种或几种的组合。
  5. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述的输运剂为碘单质及碘化物。
  6. 根据权利要求5所述的碘化物，其特征在于，碘化物为固态，包括金属碘化物和非金属碘化物。
  7. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述调控剂包括单质硫、单质硒、单质碲中的一种或几种的组合。
  8. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述加热装置为单温区管式炉、多温区(双温区及以上)管式炉、马弗炉、箱式炉、微波炉或单晶炉中的一种。
  9. 根据权利要求1所述的SiP晶体制备方法，其特征在于，所述烧结温度为900～1200℃，烧结时长12～680h。
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CN114318520A (zh) * 2020-10-09 2022-04-12 天津理工大学 基于化学气相输运法制备针状磷化硅晶体的方法
CN115491760B (zh) * 2022-09-05 2024-01-05 陕西科技大学 一种单晶Hittorf’s磷材料的制备方法

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