CN111334857B - SiP crystal growth regulation and control method - Google Patents
SiP crystal growth regulation and control method Download PDFInfo
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- CN111334857B CN111334857B CN202010217905.XA CN202010217905A CN111334857B CN 111334857 B CN111334857 B CN 111334857B CN 202010217905 A CN202010217905 A CN 202010217905A CN 111334857 B CN111334857 B CN 111334857B
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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
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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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/005—Growth of whiskers or needles
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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
- C30B29/60—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
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Abstract
The invention discloses a SiP crystal growth regulation method, and relates to single crystal material growth. The preparation method comprises the steps of sealing a silicon source, a phosphorus source, a transport agent and a regulating agent in a quartz tube in vacuum, and successfully obtaining the SiP linear monocrystal through high-temperature sintering, wherein the crystal length can reach centimeter level. The method can change the morphology of the SiP crystal by introducing a proper regulating agent, the size of the crystal is obviously increased, and the crystallinity of the crystal is greatly improved, which has important significance for obtaining high-quality single crystal SiP.
Description
Technical Field
The invention belongs to the technical field of growth regulation and control methods of single crystal materials, and particularly relates to a large-size and high-crystallinity SiP crystal growth regulation and control method.
Background
Silicon phosphide (SiP) is a P-type direct band gap semiconductor, is already a star material in the field of optical communication, and is considered as a semiconductor material with great potential for developing silicon photon technology. The band gap of bulk SiP is 1.69eV, and meanwhile, the orthogonal crystal structure of SiP tends to obtain a two-dimensional layered structure, and the band gap width of SiP increases with the thinning of the layered structure. The literature reports that nano SiP with single-layer thickness is expected to be used for blue LED luminescence, and SiP single crystal is prepared by a high-temperature melting method and used for manufacturing photoelectric devices at Shandong university.
Single crystal materials are favored because of their high crystallinity, good orientation, and stable structure. The chemical vapor transport method for preparing single crystal materials usually requires a long time and high reaction temperature when the single crystal is prepared by using raw materials and transport agents, and the single crystal can only be obtained in a small size. The invention can effectively reduce the reaction energy barrier by introducing the regulating agent, and can obtain large-size single crystals.
Disclosure of Invention
The invention aims to provide a method for effectively regulating SiP crystal growth by using a chemical vapor transport method, which adds a proper regulating agent to obtain SiP linear crystals with centimeter-level size and high crystallinity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for regulating SiP crystal growth comprises the following steps: weighing and uniformly mixing a silicon source and a phosphorus source according to the stoichiometric ratio of SiP, and adding a transport agent and a regulating agent in a certain material quantity ratio; and placing the SiP crystal into a reaction container, vacuumizing and sealing, and sintering at a high temperature in a heating device for a certain time to obtain the SiP crystal.
Further, Si in the silicon source, P in the phosphorus source, a transport agent and a regulating agent are mixed according to the mass ratio of 1: 1: 0.005-0.5: 0.01-0.1 weight percent.
Further, the silicon source is one or a combination of more of crystalline silicon, amorphous silicon and silicon tetraiodide.
Further, the phosphorus source is one or a combination of several of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide.
Further, the transport agent is one or a combination of iodine and iodide.
Further, the iodide is in a solid state and includes metal iodide and nonmetal iodide.
Further, the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium.
Further, the heating device is one of a single-temperature-zone tube furnace, a multi-temperature-zone (dual-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace.
Further, the sintering temperature is 900-1200 ℃, and the sintering time is 12-680 hours.
The SiP crystal is prepared by any one of the methods, is a linear crystal, has a length reaching the centimeter level, and has high crystallinity.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method for regulating SiP crystal growth, provided by the invention, the SiP linear single crystal with larger size, higher crystallinity and higher yield is obtained under the same sintering condition through simply introducing the regulating agent on the basis of not increasing the process complexity.
(2) The SiP crystal growth preparation method provided by the invention has the advantages of simple and mature process, wide and rich raw material sources, low price and high yield.
Drawings
Fig. 1 shows the xrd (a) and raman spectra (b) of SiP crystals in example 1 of the present invention.
FIG. 2 shows SEM (a) and SEM Mapping (b) of SiP crystals in example 1 of the present invention.
FIG. 3 is a photograph of SiP linear crystals in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of the SiP crystal material provided by the invention comprises the following steps:
(1) weighing a silicon source, a phosphorus source, a transport agent and a regulating agent in a certain proportion in a glove box, fully mixing uniformly, and transferring to a quartz tube;
(2) vacuumizing and sealing the quartz tube, and sintering the quartz tube in a heating device at a high temperature for a certain time;
(3) cooling, washing with solvent, and vacuum drying to obtain the final product.
In the above step, the mass ratio of Si in the silicon source, P in the phosphorus source, the transport agent, and the control agent in step (1) is 1: 1: (0.005-0.5): (0.01-0.1);
the silicon source is one or a combination of more of crystalline silicon, amorphous silicon and silicon tetraiodide;
the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus and phosphorus triiodide;
the transport agent is one or a combination of iodine simple substance and iodide, and the iodide is solid and comprises metal iodide and nonmetal iodide;
the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium.
The heating device in the step (2) is one of a single-temperature-zone tube furnace, a multi-temperature-zone (double-temperature-zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace or a single crystal furnace;
the calcining condition is that the temperature is set to be 900-1200 ℃, and the sintering time is 12-680 hours;
the solvents in the step (3) are acetone and ethanol respectively.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
0.14g of amorphous silicon powder, 0.16g of red phosphorus powder, 15.9mg of tellurium tetraiodide and 1.6mg of S powder are respectively weighed in a glove box, the raw materials are fully and uniformly ground, a quartz tube with the length of 11cm and the inner diameter of 11mm is added, and the quartz tube is sealed by using an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a box-type furnace, setting the furnace temperature at 1200 ℃, reacting for 12 hours, cooling the furnace body, taking out the SiP linear crystal, cleaning with acetone and ethanol, and drying in vacuum, wherein the yield of the SiP linear crystal is 92%. The crystal XRD (a) and Raman spectrum (b) are shown in figure 1. SEM (a) and SEM Mapping (b) of the SiP crystal are shown in FIG. 2. A photograph of a SiP linear crystal is shown in fig. 3.
The XRD of fig. 1a and the Raman results of fig. 1b indicate that the obtained is indeed SiP, and that the XRD peak pattern is sharp and the peak intensity is high, indicating that the crystallinity of the crystal is high. FIGS. 2a and 2b show that the atomic ratio of Si and P is 1:1 for the material, with no other impurities. FIG. 3 shows that the linear crystal size reaches the centimeter level.
Example 2
0.28g of crystalline silicon grain powder, 0.31g of fibrous phosphorus, 1.275g of iodine simple substance and 79mg of simple substance selenium are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 25cm and the inner diameter of 16mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a muffle furnace, cooling the furnace body, taking out the SiP linear crystal, cleaning the SiP linear crystal by using acetone and ethanol, and drying in vacuum, wherein the temperature of the furnace body is 900 ℃, and the reaction time is 680 hours, and finally the yield of the SiP linear crystal is 95%.
Example 3
2.68g of silicon tetraiodide, 0.16g of yellow phosphorus, 7.3mg of ammonia iodide and 32mg of tellurium powder are respectively weighed in a glove box, the raw materials are fully and uniformly ground, a quartz tube with the length of 18cm and the inner diameter of 18mm is added, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, wherein the left end temperature is 1100 ℃, the right end temperature is 1000 ℃, the raw material is in a high-temperature section, the reaction time is 350h, finally obtaining a product in a low-temperature section, washing the product with acetone and ethanol, and performing vacuum drying to obtain the final SiP linear crystal with the yield of 96%.
Example 4
0.14g of amorphous silicon powder, 2.06g of phosphorus triiodide, 14.8mg of bismuth triiodide, 2mg of sulfur and 16mg of tellurium powder are respectively weighed in a glove box, the raw materials are ground and mixed uniformly, a quartz tube with the length of 15cm and the inner diameter of 26mm is added, and the quartz tube is sealed by using an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a single crystal furnace, wherein the sintering temperature is 950 ℃, the reaction time is 96 hours, cooling the furnace body to obtain SiP linear crystals, cleaning the SiP linear crystals by using acetone and ethanol, and vacuumizing and drying the SiP linear crystals to obtain the final SiP linear crystal yield of 93%.
Comparative example 1
0.14g of amorphous silicon powder, 0.16g of red phosphorus powder and 15.9mg of tellurium tetraiodide are respectively weighed in a glove box, the amorphous silicon powder, the red phosphorus powder and the tellurium tetraiodide are not added with a regulating agent, the amorphous silicon powder, the red phosphorus powder and the tellurium tetraiodide are ground and mixed uniformly, a quartz tube with the length of 11cm and the inner diameter of 11mm is added, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a box-type furnace, setting the furnace temperature at 1200 ℃, and reacting for 12h, wherein SiP linear crystals are not found in the quartz tube after cooling, and only SiP powder samples and flocculent fibers are obtained.
Comparative example 2
0.28g of crystalline silicon grain powder, 0.31g of fibrous phosphorus and 1.275g of iodine simple substance are respectively weighed in a glove box, the raw materials are fully and uniformly ground, the raw materials are added into a quartz tube with the length of 25cm and the inner diameter of 16mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a muffle furnace, wherein the temperature is 900 ℃, the reaction time is 680h, SiP linear crystals cannot be obtained after the furnace body is cooled, and only SiP powder samples and flocculent fibers are obtained.
Comparative example 3
2.68g of silicon tetraiodide, 0.16g of yellow phosphorus and 7.3mg of ammonia iodide are weighed in a glove box respectively, the raw materials are fully and uniformly ground, the mixture is added into a quartz tube with the length of 18cm and the inner diameter of 18mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a double-temperature-zone tube furnace, wherein the left end temperature is 1100 ℃, the right end temperature is 1000 ℃, the raw material is in a high-temperature section, the reaction time is 350h, SiP linear crystals are not obtained in the quartz tube after the furnace body is cooled, and only SiP powder samples and flocculent fibers are obtained.
Comparative example 4
0.14g of amorphous silicon powder, 2.06g of phosphorus triiodide and 14.8mg of bismuth triiodide are weighed in a glove box respectively, the raw materials are ground and mixed uniformly, the mixture is added into a quartz tube with the length of 15cm and the inner diameter of 26mm, and the quartz tube is sealed by an oxyhydrogen machine after being vacuumized. And (3) placing the sealed quartz tube in a single crystal furnace, wherein the sintering temperature is 950 ℃, the reaction time is 96 hours, SiP linear crystals cannot be obtained after the furnace body is cooled, and only SiP powder samples and flocculent fibers are obtained.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for regulating SiP crystal growth is characterized by comprising the following steps: weighing and uniformly mixing a silicon source and a phosphorus source according to the stoichiometric ratio of SiP, and adding a transport agent and a regulating agent in a certain material quantity ratio; placing the SiP crystal in a reaction container, vacuumizing and sealing, and sintering at a high temperature in a heating device for a certain time to obtain SiP crystal;
si in the silicon source, P in the phosphorus source, a transport agent and a regulating agent are mixed according to the mass ratio of 1: 1: 0.005-0.5: 0.01-0.1 weight percent;
the sintering temperature is 900-1200 ℃, and the sintering time is 12-680 hours;
the transport agent is one or the combination of iodine simple substance and iodide;
the regulating agent is one or a combination of more of elemental sulfur, elemental selenium and elemental tellurium.
2. The method of claim 1, wherein the silicon source is one or more of crystalline silicon, amorphous silicon, and silicon tetraiodide.
3. The method of claim 1, wherein the phosphorus source is one or more of red phosphorus, yellow phosphorus, white phosphorus, fibrous phosphorus, purple phosphorus, and phosphorus triiodide.
4. The method of claim 1, wherein the iodide is in a solid state and comprises metallic iodide and nonmetallic iodide.
5. The method of claim 1, wherein the heating device is one of a single-temperature zone tube furnace, a multi-temperature zone (dual-temperature zone and above) tube furnace, a muffle furnace, a box furnace, a microwave furnace, or a single crystal furnace.
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CN202010217905.XA CN111334857B (en) | 2020-03-25 | 2020-03-25 | SiP crystal growth regulation and control method |
PCT/CN2020/129202 WO2021189874A1 (en) | 2020-03-25 | 2020-11-16 | Method for regulating growth of sip crystal |
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CN114318520A (en) * | 2020-10-09 | 2022-04-12 | 天津理工大学 | Method for preparing needle-shaped silicon phosphide crystals based on chemical vapor transport method |
CN115491760B (en) * | 2022-09-05 | 2024-01-05 | 陕西科技大学 | Preparation method of monocrystalline Hittorf's phosphorus material |
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CN106119960A (en) * | 2016-07-25 | 2016-11-16 | 山东大学 | Orthorhombic phase two-dimensional layer SiP monocrystalline and the preparation method and applications of thin film |
CN109295496A (en) * | 2018-09-18 | 2019-02-01 | 中国科学院合肥物质科学研究院 | A kind of synthetic method of binary phosphorus family compound-material |
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CN105506742A (en) * | 2015-12-11 | 2016-04-20 | 山东大学 | Orthorhombic-phase two-dimension-layered SiP2 single-crystal thin film, and preparation method and application thereof |
CN110424054B (en) * | 2019-09-03 | 2021-09-28 | 山东大学 | Preparation method and application of two-dimensional layered GeP single crystal nano film |
CN111334857B (en) * | 2020-03-25 | 2021-04-16 | 深圳先进技术研究院 | SiP crystal growth regulation and control method |
CN111330603A (en) * | 2020-03-25 | 2020-06-26 | 深圳先进技术研究院 | Novel efficient photocatalytic material and application thereof |
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CN106119960A (en) * | 2016-07-25 | 2016-11-16 | 山东大学 | Orthorhombic phase two-dimensional layer SiP monocrystalline and the preparation method and applications of thin film |
CN109295496A (en) * | 2018-09-18 | 2019-02-01 | 中国科学院合肥物质科学研究院 | A kind of synthetic method of binary phosphorus family compound-material |
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---|
"磷硅化合物的晶体生长与性质表征";李春龙;《中国博士学位论文全文数据库 工程科技I辑》;20190115;第38-44页 * |
Structure and growth of single crystal SiP2 using flux method;Xiang Zhang等;《Solid State Sciences》;20140823;第37卷;第1-5页 * |
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