CN105603517A - Method for growing monocrystal black phosphorus based on solid-source chemical vapor deposition method - Google Patents
Method for growing monocrystal black phosphorus based on solid-source chemical vapor deposition method Download PDFInfo
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- CN105603517A CN105603517A CN201610013415.1A CN201610013415A CN105603517A CN 105603517 A CN105603517 A CN 105603517A CN 201610013415 A CN201610013415 A CN 201610013415A CN 105603517 A CN105603517 A CN 105603517A
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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
- C30B29/02—Elements
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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
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Abstract
A method for growing monocrystal black phosphorus based on a solid-source chemical vapor deposition method includes the steps that red phosphorus, metallic tin and tin tetraiodide are placed in one end, serving as a high-temperature zone, of a sealed cavity under the vacuum condition, and the other end of the sealed cavity is reserved to serve as a low-temperature zone; then, the high-temperature zone and the low-temperature zone are respectively heated for a reaction, cooling is performed in a gradient mode, and monocrystal black phosphorus is obtained in the low-temperature zone. By means of the method, high-purity monocrystal black phosphorus can be rapidly prepared.
Description
Technical field
What the present invention relates to is a kind of technology of semi-conducting material preparation field, specifically a kind of based on solid source chemical vapor deposition methodThe method of growing single-crystal black phosphorus.
Background technology
Black phosphorus is a kind of variable semiconductor material of electrology characteristic excellence. Compared with Graphene, black phosphorus has energy gap and has with siliconGood compatibility, has huge potential in the exploitation of the components and parts such as its ballistic transistor on the scene, optical-electrical converter, secondary cellUsing value. Traditional preparation method of black phosphorus is by white phosphorus under high pressure, or makes catalyst with mercury under normal pressure, does with a small amount of black phosphorusFor crystal seed, under 493～643 Kelvins, heat 8 days, manufacturing cycle is long, purity is low, unstable properties.
Through the retrieval of prior art is found, Chinese patent literature CN105133009A, open (bulletin) day 2015.12.9,The preparation method who discloses a kind of rhombic system black phosphorus monocrystalline, the method comprises: be provided with the first area and second being interconnectedIn the reaction system in region, and under vacuum condition, red phosphorus, metallic tin and elemental iodine are carried out in the first area of reaction systemHaptoreaction, wherein, in described haptoreaction process, rises to 550-800 DEG C by the temperature of the first area of described reaction system,The temperature of the second area of described reaction system is risen to 400-700 DEG C, and the temperature of the first area of described reaction system is risen toThan the high temperature of the second area of described reaction system. The black phosphorus difficult quality of this technology based on the growth of elemental iodine catalyst meets workIndustry Technology Need.
Chinese patent literature CN104310326A, open (bulletin) day 2015.1.28, discloses one and has had high conversionBlack phosphorus preparation method, comprise the steps: that by red phosphorus, tin and tin tetraiodide be the ratio of 1～6:40～50:1～2 in mass ratioMix, pack in quartz ampoule, be evacuated to quartzy intraductal pressure and be less than 0.05pa, tube sealing, heating makes quartz ampoule Raw end temperatureBe 100 DEG C～400 DEG C, then in 1～2 hour, be warming up to 400 DEG C～700 DEG C, be incubated 5～10 hours, then 6～8In hour, be cooled to 200 DEG C～500 DEG C, be incubated 1 to 3 day, finally in 10～15 hours, be cooled to room temperature, obtain black phosphorus.The black phosphorus that this technology relates to required shortest time of growing exceedes 24h, is difficult to realize produce fast on a large scale.
Summary of the invention
The present invention is directed to prior art above shortcomings, proposed a kind of black based on solid source chemical vapor deposition method growing single-crystalThe method of phosphorus, can realize the quick preparation of high-purity black phosphorus.
The present invention is achieved by the following technical solutions,
The present invention one end by red phosphorus, metallic tin and tin tetraiodide being placed in to annular seal space under vacuum condition is as high-temperature region, andThe other end of reserved annular seal space is as low-temperature space; Then heat high-temperature region respectively and low-temperature space reacts, and adopt gradient mode to enterRow cooling, obtains monocrystalline black phosphorus at low-temperature space.
The parts by weight ratio of described red phosphorus, metallic tin and tin tetraiodide is 10～100:1～10:1, wherein catalyst tin and fourThe proportioning of stannic iodide is to affect key factor prepared by black phosphorus.
Described high-temperature region and low-temperature space independently heat up, synchronously cooling, preferably realize by quartz ampoule bottle, are specially: by stoneOne end of English ampoule bottle is as high-temperature region, and the other end is as low-temperature space, and wherein cooling is controlled as affecting key factor prepared by black phosphorus.
In described gradient cooling mode, temperature-fall period is to lower the temperature 10 DEG C in 5～10min, and the holding stage time is 0.5～2h.
Described high-temperature region and the temperature difference of low-temperature space are 1～200 DEG C.
Its maximum temperature of described heating is 450～1000 DEG C.
Described growth time is 8～160h.
The present invention relates to the monocrystalline black phosphorus that said method prepares, purity reaches 99%, and its XRD test spectral line peak position is positioned at(020)、(040)、(060)。
The present invention relates to the application of above-mentioned monocrystalline black phosphorus, can be used for preparation: field-effect transistor, diode, solar photovoltaicPond, photoelectric detector.
Technique effect
Compared with prior art, the present invention can realize the quick preparation of high-purity monocrystalline black phosphorus. Purity can arrive 99%, preparation weekPhase is 8h～160h, has remarkable lifting with respect to required 8 days these technical efficiency of preparation time of conventional method.
Brief description of the drawings
Fig. 1 is black phosphorus pictorial diagram prepared by embodiment 1.
Fig. 2 is black phosphorus SEM figure prepared by embodiment 1.
Fig. 3 is black phosphorus XRD test spectrogram prepared by embodiment 1.
Fig. 4 is black phosphorus Raman test spectrogram prepared by embodiment 1.
Detailed description of the invention
In following examples, all use: the red phosphorus of purity 99.999%, the Aladdin of purity 99.999%; Tin, purity 99.998%AlfaAesar; Tin tetraiodide; Quartz ampoule bottle length is 8-14cm.
Embodiment 1
The present embodiment comprises the following steps:
S1, after red phosphorus, metallic tin and tin tetraiodide are fully mixed in the parts by weight ratio of 10～100:1～10:1, be sealed inQuartz ampoule bottle one end, using this end as high-temperature region, the other end is as low-temperature space; Be evacuated in quartz ampoule bottle pressure lower than0.01Pa；
S2, the high-temperature region of quartz ampoule bottle is placed in to Muffle furnace high-temperature heating district, low-temperature space is placed in Muffle furnace low-temperature heat and distinguishesDo not heat; High-temperature heating district is warming up to 500 DEG C with the speed of 500 DEG C/h from 23 DEG C of room temperatures, and low-temperature heat district is with 460 DEG C/ h speed is warming up to 460 DEG C from 23 DEG C of room temperatures, keeps high-temperature heating district and low-temperature heat district temperature difference 0.5h;
S3, after 0.5h insulation finishes, within the 0.5h time, lower the temperature 10 DEG C, after insulation 0.5h, continue the above speed cooling of stating, adoptBe cooled to 200 DEG C by the gradient cooling mode of " cooling-insulation-cooling ", after be down to room temperature with stove, Zong growth time is 8h.
Be illustrated in figure 1 and prepare black phosphorus optical photograph.
If Fig. 2 is the black phosphorus SEM figure of preparation.
If Fig. 3 is the black phosphorus XRD test spectrogram of preparation.
If Fig. 4 is the black phosphorus Raman test spectrogram of preparation.
Embodiment 2
The present embodiment comprises the following steps:
S1, after red phosphorus, metallic tin and tin tetraiodide are fully mixed in the parts by weight ratio of 10～100:1～10:1, be sealed inQuartz ampoule bottle one end, using this end as high-temperature region, the other end is as low-temperature space; Be evacuated in quartz ampoule bottle pressure lower than0.01Pa；
S2, the high-temperature region of quartz ampoule bottle is placed in to Muffle furnace high-temperature heating district, low-temperature space is placed in Muffle furnace low-temperature heat and distinguishesDo not heat; High-temperature heating district is warming up to 700 DEG C with the speed of 700 DEG C/h from 23 DEG C of room temperatures, and low-temperature heat district is with 600 DEG C/ h speed is warming up to 600 DEG C from 23 DEG C of room temperatures, keeps high-temperature heating district and low-temperature heat district temperature difference 1h;
S3, after 1h insulation finishes, within the 1h time, lower the temperature 10 DEG C, after insulation 0.5h, continue the above speed cooling of stating, adopt and " fallTemperature-insulation-cooling " gradient cooling mode be cooled to 200 DEG C, after be down to room temperature with stove, Zong growth time is 24h.
Embodiment 3
The present embodiment comprises the following steps:
S1, after red phosphorus, metallic tin and tin tetraiodide are fully mixed in the parts by weight ratio of 10～100:1～10:1, be sealed inQuartz ampoule bottle one end, using this end as high-temperature region, the other end is as low-temperature space; Be evacuated in quartz ampoule bottle pressure lower than0.01Pa；
S2, the high-temperature region of quartz ampoule bottle is placed in to Muffle furnace high-temperature heating district, low-temperature space is placed in Muffle furnace low-temperature heat and distinguishesDo not heat; High-temperature heating district is warming up to 1000 DEG C with the speed of 1000 DEG C/h from 23 DEG C of room temperatures, and low-temperature heat district is with 800 DEG C/ h speed is warming up to 800 DEG C from 23 DEG C of room temperatures, keeps high-temperature heating district and low-temperature heat district temperature difference 5h;
S3, after 5h insulation finishes, within the 5h time, lower the temperature 10 DEG C, after insulation 0.5h, continue the above speed cooling of stating, adopt and " fallTemperature-insulation-cooling " gradient cooling mode be cooled to 200 DEG C, after be down to room temperature with stove, Zong growth time is 160h.
Above-mentioned concrete enforcement can by those skilled in the art under the prerequisite that does not deviate from the principle of the invention and aim in a different mannerIt is carried out to part adjustment, and protection scope of the present invention is as the criterion with claims and can't help above-mentioned concrete enforcement and limit, in its scopeEach interior implementation is all subject to the present invention's constraint.
Claims (7)
1. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus, is characterized in that, by under vacuum conditionOne end that red phosphorus, metallic tin and tin tetraiodide are placed in to annular seal space is as high-temperature region, and the other end of reserved annular seal space is as low-temperature space;Then heat high-temperature region respectively and low-temperature space reacts, and adopt gradient mode to lower the temperature, obtain monocrystalline black phosphorus at low-temperature space.
2. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteThe parts by weight ratio of red phosphorus, metallic tin and the tin tetraiodide of stating is 10～100:1～10:1.
3. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteThe high-temperature region of stating and low-temperature space independently heat up, synchronously cooling.
4. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteIn the gradient cooling mode of stating, temperature-fall period is to lower the temperature 10 DEG C in 5～10min, and the holding stage time is 0.5～2h.
5. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteThe high-temperature region of stating and the temperature difference of low-temperature space are 1～200 DEG C.
6. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteIts maximum temperature of the heating of stating is 450～1000 DEG C.
7. the method based on solid source chemical vapor deposition method growing single-crystal black phosphorus according to claim 1, is characterized in that instituteThe growth time of stating is 8～160h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498492A (en) * | 2016-11-01 | 2017-03-15 | 南京工业大学 | A kind of method for preparing rhombic system black phosphorus monocrystalline |
| CN107359341A (en) * | 2017-07-26 | 2017-11-17 | 青岛大学 | A kind of one-step method synthesizes the method and its application of black phosphorus on carbon paper |
| CN107447193A (en) * | 2016-11-14 | 2017-12-08 | 深圳大学 | A kind of black phosphorus film and preparation method thereof |
| CN108059138A (en) * | 2017-12-11 | 2018-05-22 | 昆明理工大学 | A kind of preparation method of high-purity black phosphorus |
| CN109786483A (en) * | 2018-12-18 | 2019-05-21 | 西安电子科技大学 | Photodetector and preparation method thereof based on BP material |
| CN109913942A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A kind of method that vapor transportation method prepares black phosphorus and adulterates black phosphorus monocrystalline |
| CN109970036A (en) * | 2019-05-14 | 2019-07-05 | 闽江学院 | A kind of method that nucleus assisted with high-temperature difference method quickly prepares black phosphorus |
| CN110331442A (en) * | 2019-08-07 | 2019-10-15 | 深圳市中科墨磷科技有限公司 | A kind of additional thermal field device of aided two-dimensional black phosphorus crystal growth and its application |
| CN111254494A (en) * | 2020-03-27 | 2020-06-09 | 李旻鸶 | Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus |
| CN113493929A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wafer |
| CN113493928A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wire |
| CN114293146A (en) * | 2022-03-07 | 2022-04-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498492A (en) * | 2016-11-01 | 2017-03-15 | 南京工业大学 | A kind of method for preparing rhombic system black phosphorus monocrystalline |
| CN107447193A (en) * | 2016-11-14 | 2017-12-08 | 深圳大学 | A kind of black phosphorus film and preparation method thereof |
| CN107359341A (en) * | 2017-07-26 | 2017-11-17 | 青岛大学 | A kind of one-step method synthesizes the method and its application of black phosphorus on carbon paper |
| CN108059138A (en) * | 2017-12-11 | 2018-05-22 | 昆明理工大学 | A kind of preparation method of high-purity black phosphorus |
| CN109913942A (en) * | 2018-04-18 | 2019-06-21 | 清华-伯克利深圳学院筹备办公室 | A kind of method that vapor transportation method prepares black phosphorus and adulterates black phosphorus monocrystalline |
| CN109786483A (en) * | 2018-12-18 | 2019-05-21 | 西安电子科技大学 | Photodetector and preparation method thereof based on BP material |
| CN109970036A (en) * | 2019-05-14 | 2019-07-05 | 闽江学院 | A kind of method that nucleus assisted with high-temperature difference method quickly prepares black phosphorus |
| CN110331442A (en) * | 2019-08-07 | 2019-10-15 | 深圳市中科墨磷科技有限公司 | A kind of additional thermal field device of aided two-dimensional black phosphorus crystal growth and its application |
| CN113493929A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wafer |
| CN113493928A (en) * | 2020-03-18 | 2021-10-12 | 深圳市中科墨磷科技有限公司 | Preparation method of black phosphorus single crystal wire |
| CN111254494A (en) * | 2020-03-27 | 2020-06-09 | 李旻鸶 | Preparation method for realizing cheap black phosphorus single crystal by using low-purity red phosphorus |
| CN114293146A (en) * | 2022-03-07 | 2022-04-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Black phosphorus and preparation method and application thereof |
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