CN113737279A - Preparation method of black phosphorus arsenic crystal - Google Patents
Preparation method of black phosphorus arsenic crystal Download PDFInfo
- Publication number
- CN113737279A CN113737279A CN202111066810.3A CN202111066810A CN113737279A CN 113737279 A CN113737279 A CN 113737279A CN 202111066810 A CN202111066810 A CN 202111066810A CN 113737279 A CN113737279 A CN 113737279A
- Authority
- CN
- China
- Prior art keywords
- arsenic
- temperature
- black phosphorus
- low
- tin iodide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 72
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000013078 crystal Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 7
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims abstract description 63
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 12
- CTNCAPKYOBYQCX-UHFFFAOYSA-N [P].[As] Chemical compound [P].[As] CTNCAPKYOBYQCX-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 239000011135 tin Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 229910052718 tin Inorganic materials 0.000 description 14
- 239000010931 gold Substances 0.000 description 9
- 239000010453 quartz Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- 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
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本发明公开了一种黑磷砷晶体的制备方法，保护性气氛或真空的密闭容器中，将灰砷、红磷和碘化锡混合后置于高温反应区域进行反应，并同步于低温沉积区域结晶沉积得到黑磷砷晶体；所述高温反应区域的温度不低于550℃，低温沉积区域的温度为450～530℃。本发明仅仅以低掺量的碘化锡作为添加剂，其同时作为矿化剂与传输剂，再协同高温反应区域和低温沉积区域的温度的严格控制，直接实现块状黑磷砷晶体的可控合成，得到的块状黑磷砷晶体尺寸可达到2‑3cm，杂质量少，结晶度高，呈现出(010)单一晶面族择优生长的趋势。The invention discloses a method for preparing black phosphorus arsenic crystal. In a protective atmosphere or a vacuum airtight container, gray arsenic, red phosphorus and tin iodide are mixed and then placed in a high temperature reaction area for reaction, which is synchronized in a low temperature deposition area Crystal deposition obtains black phosphorus arsenic crystals; the temperature of the high temperature reaction zone is not lower than 550°C, and the temperature of the low temperature deposition zone is 450-530°C. The present invention only uses low-dosage tin iodide as an additive, which acts as a mineralizer and a transfer agent at the same time, and cooperates with the strict control of the temperature of the high-temperature reaction area and the low-temperature deposition area to directly realize the controllable control of the massive black phosphorus arsenic crystals. Synthesized, the obtained bulk black phosphorus arsenic crystal size can reach 2-3cm, the impurity content is low, the crystallinity is high, and the (010) single crystal face family has the tendency of preferential growth.
Description
Technical Field
The invention belongs to the technical field of preparation of high-end arsenic materials, and particularly relates to a preparation method of a black phosphorus arsenic crystal.
Background
The most advanced mid-and long-wavelength infrared detectors usually select narrow bandgap semiconductors such as tellurium-cadmium-amalgam or group III to V element based quantum well or quantum dot structure materials. However, these materials currently suffer from several important challenges in their wide-spread application. First, the growth conditions for these materials are often very complex, which makes them difficult to flexibly integrate with other semiconductors; secondly, even after the detector is manufactured, the requirement of high working environment (low temperature and stability) is met, and the use of the detector in most environments is limited under the condition of lacking complex refrigeration equipment. The discovery of the graphene provides a new idea for the application of the medium-long wave infrared detector under the room temperature condition: the two-dimensional material is applied to the manufacture of the medium-long wave infrared detector. However, the inherent zero band gap and extremely low light absorption of graphene can result in extremely high dark current and noise levels, limiting its practical application in the field of infrared detection. Currently, high performance mid-and long-wavelength infrared photodetectors capable of operating at room temperature have not been available. The black phosphorus arsenic can reach a band gap of 0.15-0.3eV by adjusting components, which means that the black phosphorus arsenic not only completely covers the middle wavelength infrared region of the spectrum, but also extends to the long wavelength infrared region (8-14 microns), and the two-dimensional material of the black phosphorus arsenic also has high carrier mobility and high on-off ratio characteristics, has unique potential which cannot be replaced in the infrared detection field, and gives new hope to the optical application of the long wavelength infrared region under the room temperature condition.
The black phosphorus-arsenic has an orthogonal lattice with a wrinkled honeycomb structure, and has strong in-plane covalent bonds and weak inter-layer van der Waals' effect, wherein the arsenic atoms and phosphorus atoms are distributed in a manner that the content of arsenic atoms is 0<As is less than or equal to 0.83, the unit cell volume of the black phosphorus arsenic crystal is in direct proportion to the proportion of arsenic atoms, and the lattice constant is usually b > c > a, wherein a, b and c are the lattice constants along the directions of zigzag, stacking and armchairs respectively. At present, a top-down method is a mainstream method for preparing black phosphorus and arsenic two-dimensional materials, and is generally a method for synthesizing black phosphorus and arsenic crystals by a chemical vapor transport method, and then the black phosphorus and arsenic two-dimensional materials are obtained by mechanical stripping or liquid phase stripping. Wherein, the synthesis of high-quality black phosphorus arsenic crystalIs key, and the existing gas-phase synthesis method mainly uses tin (Sn) and tin iodide (SnI)4) As a transmission agent, the doping of a large amount of Sn leads to high-tin-content impurities entering the black phosphorus arsenic material, so that the synthesis of the black phosphorus arsenic material with high quality and high purity is difficult to realize.
Disclosure of Invention
The invention aims to solve the technical problem that the synthesis of a high-quality and high-purity black phosphorus arsenic material is difficult to realize due to the large doping of Sn in the existing black phosphorus arsenic preparation process, and provides a preparation method of a black phosphorus arsenic crystal, wherein only tin iodide (SnI) with relatively low doping amount is used4) As a single transmission agent, the controllable synthesis of the black phosphorus arsenic crystal is realized.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a method for preparing black phosphorus-arsenic crystal comprises adding ash arsenic (As), red phosphorus (P) and tin iodide (SnI) in protective atmosphere or vacuum sealed container4) Mixing, placing the mixture in a high-temperature reaction area for reaction, and synchronously crystallizing and depositing in a low-temperature deposition area to obtain black phosphorus arsenic crystals; the temperature of the high-temperature reaction area is not lower than 550 ℃, and the temperature of the low-temperature deposition area is 450-530 ℃.
Preferably, the atomic ratio of the ash arsenic (As) to the red phosphorus (P) is 3: 1-1: 4; further preferably, the atomic ratio is 2:1 to 1: 1.
Preferably, the tin iodide (SnI)4) The addition amount of the additive is 1-4 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide; further preferably, the addition amount is 2-3 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
Preferably, the temperature of the high-temperature reaction area is 550-650 ℃, and the temperature of the low-temperature deposition area is 490-500 ℃.
Preferably, the reaction time is at least 12 h; further preferably 20 to 24 hours.
In the invention, raw materials of ash arsenic (As), red phosphorus (P) and transport agent of tin iodide (SnI)4) Gasifying at the temperature of the high-temperature reaction area, transferring the formed gaseous product to the low-temperature area under the pushing of the temperature difference gradient, and crystallizing and depositing arsenic and phosphorus at the temperature of the low-temperature deposition area to obtainWhen the black phosphorus arsenic product is obtained, the gaseous iodide returns to the high-temperature reaction region under the pushing of the concentration difference, so that the transmission process is continuously carried out, and the low-doped tin iodide (SnI)4) Meanwhile, the crystal is used as a mineralizer and a transmission agent to realize the controllable synthesis of the blocky black phosphorus arsenic crystal.
The invention has the advantages that:
1. the invention avoids large amount of tin (Sn) and tin iodide (SnI)4) Adding raw material of ash arsenic (As) and red phosphorus (P) with only low doping amount of tin iodide (SnI)4) As an additive, the tin doping amount is only 0.19-0.75 wt%, which is far lower than the high tin doping amount (more than 5 wt%) required by other black phosphorus and arsenic synthesis methods. Small amount of tin iodide (SnI)4) The crystal is used as a mineralizer and a transmission agent, and is cooperated with the strict control of the temperature of a high-temperature reaction area and a low-temperature deposition area to directly realize the controllable synthesis of the massive black phosphorus arsenic crystal.
2. The size of the blocky black phosphorus arsenic crystal obtained by the invention can reach 2-3cm, the impurity amount is small, the crystallinity is high, and the trend of preferential growth of a single crystal face family (010) is presented.
Drawings
FIG. 1 is a schematic view of the gas phase reaction principle of the present invention;
FIG. 2 is a graph comparing X-ray diffraction (XRD) results of bulk black phosphorus arsenic prepared under different As-P atomic ratios in example 1 of the present invention;
FIG. 3 is a diagram of a bulk black phosphorus arsenic prepared in example 1 of the present invention with an As-P atomic ratio of 1: 1;
FIG. 4 is a Scanning Electron Microscope (SEM) image of bulk black arsenic phosphide prepared with an As-P atomic ratio of 1:1 in example 1 of the present invention;
FIG. 5 is an X-ray diffraction (XRD) pattern of bulk black phosphorus arsenic prepared according to example 1 of the present invention with an As-P atomic ratio of 1: 1;
FIG. 6 is a Raman spectrum (Raman) chart of bulk black phosphorus arsenic prepared with an As-P atomic ratio of 1:1 in example 1 of the present invention;
FIG. 7 is a comparison graph of X-ray diffraction (XRD) results of bulk black phosphorus arsenic prepared under different addition amounts of transport agents when the As-P atomic ratio is 1:1 in examples 1-5 of the present invention;
FIG. 8 is a graph comparing the X-ray diffraction (XRD) results of the bulk black phosphorus arsenic prepared under different types of transport agents in example 1 and comparative examples 1-3.
Detailed Description
The invention is illustrated below with reference to examples, but the scope of protection of the invention is not limited to the examples.
Example 1
Step 1: cleaning the quartz tube with 2% hydrofluoric acid; the raw materials of arsenic (As) and red phosphorus (P) are ground into powder for standby.
Step 2: weighing ash arsenic (As) and red phosphorus (P) with a certain atomic ratio by using a ten-thousandth electronic balance As raw materials in an inert atmosphere of a glove box, and adding the raw materials into a quartz tube;
and step 3: 3 wt% tin iodide (SnI) was weighed in a glove box under an inert atmosphere using a ten thousandth electronic balance4) As a transmission agent, is added into a quartz tube;
and 4, step 4: plugging one end of the quartz tube by using a plug, then sealing the quartz tube by using a vacuum valve, and then taking the quartz tube out of the glove box;
and 5: vacuumizing the quartz tube by using a tube sealing machine, and sealing the quartz tube by using an oxyhydrogen machine;
step 6: horizontally placing the sealed quartz tube in a multi-temperature-zone tube furnace, setting the temperature of a double-temperature zone, then carrying out gas-phase synthesis reaction, wherein the temperature of a high-temperature reaction zone is 550 ℃, the temperature of a low-temperature deposition zone is 500 ℃, keeping the temperature for 20h, then cooling to 150 ℃, and finally naturally cooling to room temperature.
Taking the reaction system of example 1 As an example, XRD results of black phosphorus arsenic materials synthesized with different As-P atomic ratios are shown in FIG. 2, and it can be seen from the figure that black phosphorus arsenic materials can be obtained with As-P atomic ratios ranging from 3:1 to 1:4, preferably 2:1 to 1:1, and most preferably 1: 1.
In this example, the As-P atomic ratio of the synthesized material is 1:1 As shown in fig. 3; SEM results are shown in FIG. 4; the XRD results are shown in FIG. 5; the Raman results are shown in figure 6.
Example 2
As in example 1, the As-P atomic ratio was 1:1, differing only in thatTransport agent tin iodide (SnI)4) The addition amount of the additive is 4 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
Example 3
As-P in example 1, the atomic ratio As-P was 1:1, except that the transport agent tin iodide (SnI)4) The addition amount of the additive is 2 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
Example 4
As-P in example 1, the atomic ratio As-P was 1:1, except that the transport agent tin iodide (SnI)4) The addition amount of the additive is 1.5 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
Example 5
As-P in example 1, the atomic ratio As-P was 1:1, except that the transport agent tin iodide (SnI)4) The addition amount of the additive is 1 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
Comparative example 1
As-P in example 1, the atomic ratio As-P was 1:1, except that the transport agent tin iodide (SnI)4) Is added in an amount of 0%, i.e., tin iodide (SnI) is not added4)。
Comparative example 2
As-P in example 1, the atomic ratio As-P was 1:1, except that the transport agents were tin (Sn) and tin iodide (SnI)4) Wherein tin iodide (SnI)4) The addition amount of (A) is 3 wt% of the total mass of the ash arsenic, red phosphorus, tin and tin iodide, and the addition amount of (Sn) is 12 wt% of the total mass of the ash arsenic, red phosphorus, tin and tin iodide.
Comparative example 3
As-P atomic ratio was 1:1 As in example 1, except that the transport agent was tin (Sn), tin iodide (SnI)4) And gold (Au), in which tin iodide (SnI)4) The addition amount of (A) is 3 wt% of the total mass of the ash arsenic, red phosphorus, gold, tin and tin iodide, (B) the addition amount of tin (Sn) is 12 wt% of the total mass of the ash arsenic, red phosphorus, gold, tin and tin iodide, and (C) the addition amount of gold (Au) is 16 wt% of the total mass of the ash arsenic, red phosphorus, gold, tin and tin iodide.
As shown in fig. 8, in comparative example 1, the ash arsenic (As) and red phosphorus (P) can not be converted by themselves to obtain black arsenic phosphorus crystals without the action of the transmission agent; ash arsenic of comparative example 2 (As), red phosphorus (P), tin (Sn) and tin iodide (SnI)4) System and comparative example 3 of ash arsenic (As), red phosphorus (P), tin (Sn), tin iodide (SnI)4) Although the system can realize the conversion of arsenic and phosphorus to black phosphorus arsenic material with gold (Au), the product has more impurities and poorer crystal form. The invention adopts ash arsenic (As), red phosphorus (P) and tin iodide (SnI)4) The system can also realize the conversion of arsenic and phosphorus to black phosphorus arsenic materials, and the obtained blocky black phosphorus arsenic crystal has less impurity phases and high crystallinity and has the characteristic of single crystal face family expression of (010).
Claims (8)
1. A preparation method of black phosphorus arsenic crystal is characterized by comprising the following steps: in a protective atmosphere or a vacuum closed container, mixing ash arsenic, red phosphorus and tin iodide, placing the mixture in a high-temperature reaction area for reaction, and synchronously crystallizing and depositing in a low-temperature deposition area to obtain black phosphorus arsenic crystals; the temperature of the high-temperature reaction area is not lower than 550 ℃, and the temperature of the low-temperature deposition area is 450-530 ℃.
2. The method for preparing the black phosphorus-arsenic crystal according to claim 1, wherein the method comprises the following steps: the atomic ratio of the ash arsenic to the red phosphorus is 3: 1-1: 4.
3. The method for preparing the black phosphorus-arsenic crystal according to claim 2, wherein the method comprises the following steps: the atomic ratio of the ash arsenic to the red phosphorus is 2: 1-1: 1.
4. The method for preparing the black phosphorus-arsenic crystal according to claim 1, wherein the method comprises the following steps: the addition amount of the tin iodide is 1-4 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
5. The method for preparing the black phosphorus-arsenic crystal according to claim 4, wherein the method comprises the following steps: the addition amount of the tin iodide is 2-3 wt% of the total mass of the ash arsenic, the red phosphorus and the tin iodide.
6. The method for preparing the black phosphorus-arsenic crystal according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature reaction area is 550-650 ℃, and the temperature of the low-temperature deposition area is 490-500 ℃.
7. The method for preparing the black phosphorus-arsenic crystal according to claim 1, wherein the method comprises the following steps: the reaction time is at least 12 h.
8. The method for preparing the black phosphorus-arsenic crystal according to claim 7, wherein the method comprises the following steps: the reaction time is 20-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066810.3A CN113737279B (en) | 2021-09-13 | 2021-09-13 | Preparation method of black phosphorus arsenic crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111066810.3A CN113737279B (en) | 2021-09-13 | 2021-09-13 | Preparation method of black phosphorus arsenic crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113737279A true CN113737279A (en) | 2021-12-03 |
| CN113737279B CN113737279B (en) | 2022-07-15 |
Family
ID=78738195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111066810.3A Active CN113737279B (en) | 2021-09-13 | 2021-09-13 | Preparation method of black phosphorus arsenic crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113737279B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115807211A (en) * | 2023-02-08 | 2023-03-17 | 中南大学 | Preparation method and device of arsenic-phosphorus thin film material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190055668A1 (en) * | 2016-04-01 | 2019-02-21 | Suzhou Institute of Nano- Tech and Nano-Bionics (Sinano), Chinese Academy of Sciences | Black Phosphorus Crystal Having High Photoelectric Response Rate, Two-Dimensional Black Phosphorus PN Junction, and Preparation Method and Use Thereof |
| CN109913946A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A method for preparing black arsenic phosphorus single crystal by gas-phase transport method |
| CN112093784A (en) * | 2020-09-25 | 2020-12-18 | 深圳大学 | Preparation method and application of two-dimensional black arsenic-phosphorus nano material |
-
2021
- 2021-09-13 CN CN202111066810.3A patent/CN113737279B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190055668A1 (en) * | 2016-04-01 | 2019-02-21 | Suzhou Institute of Nano- Tech and Nano-Bionics (Sinano), Chinese Academy of Sciences | Black Phosphorus Crystal Having High Photoelectric Response Rate, Two-Dimensional Black Phosphorus PN Junction, and Preparation Method and Use Thereof |
| CN109913946A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A method for preparing black arsenic phosphorus single crystal by gas-phase transport method |
| CN112093784A (en) * | 2020-09-25 | 2020-12-18 | 深圳大学 | Preparation method and application of two-dimensional black arsenic-phosphorus nano material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115807211A (en) * | 2023-02-08 | 2023-03-17 | 中南大学 | Preparation method and device of arsenic-phosphorus thin film material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113737279B (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mitzi et al. | Conducting tin halides with a layered organic-based perovskite structure | |
| Jule et al. | Wide visible emission and narrowing band gap in Cd-doped ZnO nanopowders synthesized via sol-gel route | |
| Yang et al. | Synthesis and optical properties of single-crystalline bismuth selenide nanorods via a convenient route | |
| CN108039403B (en) | Batch preparation method of high-quality wafer-level bismuth selenide semiconductor single-crystal film | |
| CN115041677B (en) | Chemical vapor deposition on mica to generate Bi 2 O 2 Te nano-sheet method | |
| US9334443B1 (en) | Synthesis of CsSnI3 by a solution based method | |
| Khimani et al. | Study of indium and antimony incorporation into SnS2 single crystals | |
| CN112301239A (en) | Preparation method of cadmium arsenide | |
| CN113737279A (en) | Preparation method of black phosphorus arsenic crystal | |
| JP2016523806A (en) | Novel form of silicon and method for producing the same | |
| CN112960660A (en) | Black phosphorus nanobelt material and preparation method thereof | |
| Zhang et al. | Room temperature growth of nanocrystalline tin (II) selenide from aqueous solution | |
| CN111876828A (en) | Two-dimensional bismuth sulfide crystal material and preparation method thereof | |
| CN115787078A (en) | A kind of preparation method of high-quality misfit layer compound | |
| Fu et al. | Synthesis, crystal structure and optical properties of Ce doped CuInSe2 powders prepared by mechanically alloying | |
| Friedman et al. | Comparison of hydrazine, dimethylhydrazine, and t-butylamine nitrogen sources for MOVPE growth of GaInNAs for solar cells | |
| Khemiri et al. | Synthesis and Characterization of CuIn 2n+ 1 S 3n+ 2 (with n= 0, 1, 2, 3 and 5) Powders | |
| CN118835309A (en) | Method for obtaining stacked superlattice based on transition metal element or chalcogen element doping and application | |
| CN113046692A (en) | Preparation method of single-crystal tungsten diselenide monolayer film | |
| CN117468095A (en) | A method for preparing ternary layered telluride and its single crystal | |
| Zhang et al. | Synthesis and characterization of a novel quaternary chalcogenide KBiCu2S3 | |
| Zhang et al. | Growth of submillimeter-scale single crystal 2D BiI3 by the cooling-induced growth method in a confined space | |
| US11761112B2 (en) | Method for preparing large-size two-dimensional layered metal thiophosphate crystal | |
| US5275966A (en) | Low temperature process for producing antimony-containing semiconductor materials | |
| CN113186590A (en) | Preparation method of centimeter-level molybdenum trioxide single crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240419 Address after: Building G5-1, Lushan Science and Technology Innovation Park, No. 966 Lushan South Road, Science Village Community, Yuelu Street, Yuelu District, Changsha City, Hunan Province, 410006 Patentee after: New Engine (Changsha) Technology Development Co.,Ltd. Country or region after: China Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University Country or region before: China |