CN115491760B - Preparation method of monocrystalline Hittorf's phosphorus material - Google Patents
Preparation method of monocrystalline Hittorf's phosphorus material Download PDFInfo
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- CN115491760B CN115491760B CN202211078200.XA CN202211078200A CN115491760B CN 115491760 B CN115491760 B CN 115491760B CN 202211078200 A CN202211078200 A CN 202211078200A CN 115491760 B CN115491760 B CN 115491760B
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 30
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 25
- 239000011630 iodine Substances 0.000 claims abstract description 25
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 23
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 14
- 239000011574 phosphorus Substances 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C30B29/02—Elements
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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)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention belongs to the technical field of preparation of single crystal Hittorf's phosphorus, and particularly relates to a preparation method of a single crystal Hittorf's phosphorus material, which comprises the following steps: under the vacuum condition, taking amorphous red phosphorus, tellurium simple substance and iodine simple substance as raw materials, and preserving heat for 288-312 min at the temperature of more than or equal to 600 ℃; then, the temperature is reduced to 480 to 488 ℃ through the first stage cooling treatment, and then the temperature is kept for 112 to 128 minutes; then cooling to 108-126 ℃ through the second stage cooling treatment, and then cooling to room temperature through the third stage cooling treatment to obtain the monocrystalline Hittorf's phosphorus material. The preparation method of the invention has safe operation, short preparation time, extremely high purity of the prepared purple phosphorus crystal, high yield up to 99.9%, convenient popularization and use and extremely wide market prospect.
Description
Technical Field
The invention relates to the technical field of preparation of single crystal Hittorf's phosphorus, in particular to a preparation method of a single crystal Hittorf's phosphorus material.
Background
The purple phosphorus is used as an allotrope of phosphorus and is a layered P-type semiconductor material. As a more stable phosphoisomorphone, the theory predicts that the hole mobility of the purple phosphorus (VP) can reach 7000cm 2 V -1 s -1 Direct band gaps in monolayers of up to 2.5eV make them ideal candidates for blue optoelectronic applications, however, it is challenging to obtain these attractive properties experimentally. For example, smaller crystals of the secondary solute tend to grow with BP, which makes separation and purification of the secondary solute difficult due to brittleness of the P-P bond and interlayer interactions between P8 cages, exfoliation of HP crystals inevitably results in thick and small fragments to the targetUntil now, only a few people tried bulk parahaemolysis with exfoliating.
However, the production of purple phosphorus single crystals has so far been limited by their yield, which has hindered the exploration and application of their single crystal properties. A reliable synthesis strategy is provided for efficiently preparing high quality single crystal violet phosphorus to overcome the disadvantages generated by prior methods.
In order to solve the above problems, one skilled in the art has proposed a method of using Sn and SnI 4 As a transfer agent, the method for preparing the purple phosphorus by reacting with the amorphous red phosphorus, but the final product obtained by the method is low in purity and yield of the purple phosphorus except the purple phosphorus and also black phosphorus, and the method for preparing the purple phosphorus is low in efficiency and cannot meet the requirements of scientific research and market at present.
Therefore, the invention provides a preparation method of a single crystal Hittorf's phosphorus material.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a single crystal Hittorf's phosphorus material. The preparation method provided by the invention is simple, has high conversion rate, and lays a road for the performance exploration and application of the single crystal purple phosphorus.
The preparation method of the monocrystalline Hittorf's phosphorus material is realized by the following technical scheme:
a preparation method of a single crystal Hittorf's phosphorus material comprises the following steps:
under the vacuum condition, taking amorphous red phosphorus, tellurium simple substance and iodine simple substance as raw materials, and preserving heat for 288-312 min at the temperature of more than or equal to 600 ℃; then, the temperature is reduced to 480 to 488 ℃ through the first stage cooling treatment, and then the temperature is kept for 112 to 128 minutes; then cooling to 108-126 ℃ through the second stage cooling treatment, and then cooling to room temperature through the third stage cooling treatment to obtain the monocrystalline Hittorf's phosphorus material.
Further, the mass ratio of the amorphous red phosphorus to the tellurium to the iodine is 1.6-10:1:1.
Further, the cooling rate of the first-stage cooling treatment is 0.25-0.32 ℃/min.
Further, the cooling rate of the second stage cooling treatment is 0.8-1.3 ℃/min.
Further, the third stage cooling treatment adopts an air cooling mode to cool to room temperature.
Further, the temperature is raised to be more than or equal to 600 ℃ at the temperature rising rate of 2-20 ℃/min.
Further, the vacuum condition is achieved by:
amorphous red phosphorus, tellurium and iodine are added to a vessel having a sealing effect, followed by vacuum sealing.
Further, the vacuum degree of the vacuum condition is less than or equal to 10 -4 Pa。
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, amorphous red phosphorus is used as a phosphorus source, elemental tellurium and elemental iodine are used as mineralizers, chemical vapor transmission treatment is carried out under a vacuum condition, and in the reaction process, the amorphous red phosphorus can form a Te-I-P intermediate with the elemental tellurium and elemental iodine to be in an activated state, so that lattice distortion and activation of the Te-I-P intermediate can be promoted, the reaction process is accelerated, and the reaction time for obtaining high-purity purple phosphorus crystals is greatly shortened.
The preparation method of the invention has safe operation, short preparation time, extremely high purity of the prepared purple phosphorus crystal, high yield up to 99.9%, convenient popularization and use and extremely wide market prospect.
Drawings
FIG. 1 is a photograph of a crystal of monocrystalline Hittorf's phosphorus prepared in accordance with the present invention;
FIG. 2 is an SEM image of single crystal Hittorf's phosphorus prepared according to the invention;
FIG. 3 is a powder X-ray diffraction pattern of single crystal Hittorf's phosphorus prepared in accordance with 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 accompanying drawings in the embodiments of the present invention.
Example 1
The embodiment provides a preparation method of a single crystal Hittorf's phosphorus material, which comprises the following steps:
step 1, respectively weighing 350mg of amorphous red phosphorus, 35mg of tellurium simple substance and 35mg of iodine simple substance in a glove box filled with nitrogen; placing the weighed 350mg of amorphous red phosphorus, 35mg of tellurium simple substance and 35mg of iodine simple substance into a vessel with a sealing function, and then carrying out vacuum sealing;
the invention is not limited to the specific vacuum degree of the vacuum seal, as long as the reaction system is in a vacuum state in the whole subsequent heat treatment process.
The invention is not limited in the heat treatment process, and the type of the vessel in which the amorphous red phosphorus, tellurium simple substance and iodine simple substance are placed can be sealed only by processing treatment. Alternatively, in this embodiment, a glass ampoule is used as a vessel for placing the amorphous red phosphorus, tellurium simple substance, and iodine simple substance.
Step 2, placing the glass ampoule subjected to vacuum sealing treatment in a muffle furnace, and then heating to above 600 ℃; reducing the temperature to 485 ℃ at the cooling rate of 0.3 ℃/min, preserving heat for 120min, reducing the temperature to 118 ℃ at the cooling rate of 1.0 ℃/min, and directly and naturally cooling to room temperature to obtain the monocrystalline Hittorf's phosphorus material;
the temperature and the heating rate of the heating temperature are not limited, and the heating rate is set within the range of 2-20 ℃/min so as to raise the temperature to above 600 ℃ and ensure that the added raw materials are completely sublimated into a gaseous state. Optionally, in this embodiment, the precursor is kept warm for 300min after being heated to 610 ℃ at a heating rate of 5 ℃/min, so as to ensure that the precursor is completely sublimated into a gaseous state.
The single crystal Hittorf's phosphorus material prepared in this example is shown in FIG. 1, and it can be seen that the single crystal Hittorf's phosphorus material prepared in this example has no obvious impurity, and the yield is calculated to be 99.9%, approaching 100%, which is improved by 64.9% compared with the yield of 36% in the prior art mentioned in the background art, and great progress is achieved.
SEM testing was also performed on the product of fig. 1 in this example, and the results are shown in fig. 2, and it can be seen that: the single crystal Hittorf's phosphorus material obtained in the embodiment has an obvious crystal structure, and the surface of the material is smooth and has no obvious impurity.
This example also performed powder X-ray diffraction testing of the product of fig. 1, and the results are shown in fig. 3, as can be seen: the single crystal Hittorf's phosphorus material prepared in this example is pure phase, which indicates that the single crystal Hittorf's phosphorus material prepared in this example has higher purity.
Example 2
The embodiment provides a preparation method of a single crystal Hittorf's phosphorus material, which comprises the following steps:
step 1, respectively weighing 100mg of amorphous red phosphorus, 10mg of tellurium simple substance and 10mg of iodine simple substance in a glove box filled with nitrogen; placing 100mg of amorphous red phosphorus, 10mg of tellurium simple substance and 10mg of iodine simple substance in a vessel with sealing function, and then carrying out vacuum sealing;
step 2, placing the glass ampoule subjected to vacuum sealing treatment in a muffle furnace, then heating to 605 ℃ at a heating rate of 5 ℃/min, and preserving heat for 288min; the temperature is reduced to 480 ℃ at the cooling rate of 0.25 ℃/min, the temperature is kept for 112min, the temperature is reduced to 108 ℃ at the cooling rate of 0.8 ℃/min, and the monocrystalline Hittorf's phosphorus material is obtained after cooling to room temperature.
The yield of the single crystal Hittorf's phosphorus material obtained in this example was 98.5%.
Example 3
The embodiment provides a preparation method of a single crystal Hittorf's phosphorus material, which comprises the following steps:
step 1, respectively weighing 600mg of amorphous red phosphorus, 60mg of tellurium simple substance and 60mg of iodine simple substance in a glove box filled with nitrogen; placing 600mg of the weighed amorphous red phosphorus, 60mg of tellurium simple substance and 60mg of iodine simple substance into a vessel with a sealing function, and then carrying out vacuum sealing;
step 2, placing the glass ampoule subjected to vacuum sealing treatment in a muffle furnace, then heating to 650 ℃ at a heating rate of 5 ℃/min, and preserving heat for 312min; reducing the temperature to 488 ℃ at the cooling rate of 0.32 ℃/min, preserving the heat for 128min, reducing the temperature to 126 ℃ at the cooling rate of 1.3 ℃/min, and cooling to room temperature to obtain the monocrystalline Hittorf's phosphorus material.
The yield of the single crystal Hittorf's phosphorus material obtained in this example was 99.1%.
Example 4
This example provides a method for preparing single crystal Hittorf's phosphorus material, which differs from example 1 in that:
in this example, the temperature was raised to 610℃at a heating rate of 2℃per minute.
In this example, 100mg of amorphous red phosphorus, 90mg of elemental tellurium and 90mg of elemental iodine were weighed separately.
The yield of the single crystal Hittorf's phosphorus material obtained in this example was 94%.
Example 5
This example provides a method for preparing single crystal Hittorf's phosphorus material, which differs from example 1 in that:
in this example, the temperature was raised to 610℃at a heating rate of 20℃per minute.
In this example, 600mg of amorphous red phosphorus, 10mg of elemental tellurium and 10mg of elemental iodine were weighed respectively.
The yield of single crystal Hittorf's phosphorus material obtained in this example was 85%.
Comparative example 1
This comparative example provides a method for preparing single crystal Hittorf's phosphorus material, which differs from example 1 in that:
in this comparative example, the temperature was raised to 560 ℃.
The yield of the single crystal Hittorf's phosphorus material obtained in this comparative example was 60%.
Compared with the embodiment 1, the yield of the single crystal Hittorf's phosphorus material prepared by the comparative example is greatly reduced, which shows that the temperature rising in the temperature rising stage plays an important role in preparing the single crystal Hittorf's phosphorus material with high purity and high yield, the temperature needs to be raised to be higher than 600 ℃, the added raw materials can be ensured to be completely sublimated into a gaseous state, and then the amorphous red phosphorus can almost completely form the single crystal Hittorf's phosphorus material under the action of a tellurium simple substance and an iodine simple substance.
Comparative example 2
This comparative example provides a method for preparing single crystal Hittorf's phosphorus material, which differs from example 1 in that:
in this comparative example, no elemental iodine was added.
The yield of the single crystal Hittorf's phosphorus material obtained in this comparative example was 0%.
According to the comparative example, under the condition that an iodine simple substance is not added, the single crystal Hittorf's phosphorus material cannot be prepared, and the fact that the iodine simple substance is an important mineralizer, and the absence of the iodine simple substance leads to the formation of a Te-I-P intermediate, so that the whole reaction system cannot be effectively activated, and the single crystal Hittorf's phosphorus material is difficult to prepare. This also demonstrates on the side that the formation of the Te-I-P intermediate during the reaction of the present invention is the most critical part in the successful preparation of single crystal Hittorf's phosphorus materials.
Comparative example 3
This comparative example provides a method for preparing single crystal Hittorf's phosphorus material, which differs from example 1 in that:
in this comparative example, the simple substance of tellurium was replaced with the simple substance of tin.
The yield of the single crystal Hittorf's phosphorus material obtained in this comparative example was 10%.
This comparative example replaces elemental tellurium with elemental tin of the prior art, resulting in a single crystal Hittorf's phosphorus material prepared in a yield far lower than that of example 1, but also far lower than that of 36% of the prior art. This is probably due to the difference in properties between the elemental tin and the elemental tellurium itself, resulting in the inability of the elemental tin to form with the elemental iodine an "Sn-I-P intermediate" with amorphous red phosphorus similar to the "Te-I-P intermediate", and thus in a low yield of monocrystalline hitdorf's phosphorus material. This further illustrates that the formation of Te-I-P intermediates during the reaction of the present invention is the most critical part in the successful preparation of high purity and high yield single crystal Hittorf's phosphorus materials.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (8)
1. A method for preparing a single crystal Hittorf's phosphorus material, which is characterized by comprising the following steps:
under the vacuum condition, taking amorphous red phosphorus, tellurium simple substance and iodine simple substance as raw materials, and preserving heat for 288-312 min at the temperature of more than or equal to 600 ℃; then, the temperature is reduced to 480 to 488 ℃ through the first stage cooling treatment, and then the temperature is kept for 112 to 128 minutes; then cooling to 108-126 ℃ through the second stage cooling treatment, and then cooling to room temperature through the third stage cooling treatment to obtain the monocrystalline Hittorf's phosphorus material.
2. The preparation method as claimed in claim 1, wherein the mass ratio of amorphous red phosphorus, tellurium and iodine is 1.6-10:1:1.
3. The method according to claim 1, wherein the first-stage cooling treatment is performed at a cooling rate of 0.25 to 0.32 ℃/min.
4. The method according to claim 1, wherein the second-stage cooling treatment is performed at a cooling rate of 0.8 to 1.3 ℃/min.
5. The method according to claim 1, wherein the third-stage cooling process is performed by cooling to room temperature by air cooling.
6. The process according to claim 1, wherein the temperature is raised to at least 600 ℃ at a temperature-raising rate of 2 to 20 ℃/min.
7. The method of claim 1, wherein the vacuum condition is achieved by:
amorphous red phosphorus, tellurium and iodine are added to a vessel having a sealing effect, followed by vacuum sealing.
8. The method according to claim 6, wherein the vacuum condition has a vacuum degree of 10 or less -4 Pa。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200001307A (en) * | 2018-06-27 | 2020-01-06 | 국민대학교산학협력단 | Fabrication method of pure black phosphorus single crystal |
| CN110938867A (en) * | 2019-12-06 | 2020-03-31 | 深圳市中科墨磷科技有限公司 | Method for efficiently preparing two-dimensional black phosphorus crystal |
| CN111334857A (en) * | 2020-03-25 | 2020-06-26 | 深圳先进技术研究院 | SiP crystal growth regulation and control method |
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200001307A (en) * | 2018-06-27 | 2020-01-06 | 국민대학교산학협력단 | Fabrication method of pure black phosphorus single crystal |
| CN110938867A (en) * | 2019-12-06 | 2020-03-31 | 深圳市中科墨磷科技有限公司 | Method for efficiently preparing two-dimensional black phosphorus crystal |
| CN111334857A (en) * | 2020-03-25 | 2020-06-26 | 深圳先进技术研究院 | SiP crystal growth regulation and control method |
| CN112960660A (en) * | 2021-04-27 | 2021-06-15 | 陕西科技大学 | Black phosphorus nanobelt material and preparation method thereof |
| CN113957524A (en) * | 2021-11-02 | 2022-01-21 | 陕西科技大学 | Crystal red phosphorus fiber and efficient preparation method thereof |
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