CN112429703B - Two-dimensional layered tellurium-doped germane and preparation method thereof - Google Patents
Two-dimensional layered tellurium-doped germane and preparation method thereof Download PDFInfo
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- CN112429703B CN112429703B CN201910792265.2A CN201910792265A CN112429703B CN 112429703 B CN112429703 B CN 112429703B CN 201910792265 A CN201910792265 A CN 201910792265A CN 112429703 B CN112429703 B CN 112429703B
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Abstract
The invention discloses a two-dimensional layered tellurium-doped germane and a preparation method thereof, which comprises the steps of packaging Ca, geTe and Ge in a tube furnace according to stoichiometric ratio and carrying out temperature program control to obtain CaGe 2‑2x Te 2x (x = 0.01-0.05) precursor, and reacting the obtained precursor with hydrochloric acid at low temperature to obtain the two-dimensional layered semiconductor material tellurium-doped germane HGe 1‑x Te x (x = 0.01-0.05). The two-dimensional material has great potential application in photoelectric devices, energy storage, photocatalysis and the like.
Description
Technical Field
The invention relates to preparation of doped two-dimensional layered germane, belongs to the technical field of preparation of two-dimensional germanium-based semiconductor materials, and particularly relates to two-dimensional layered tellurium-doped germane and a preparation method thereof.
Background
Since the emergence of graphene in 2004, various novel two-dimensional materials are emerging continuously, and have great application potential in the fields of photoelectric devices, photocatalysis, energy storage and the like. Graphene has ultrahigh electron mobility, but its zero band gap limits its application to field effect transistors and the like. Transition metal sulfides such as MoS 2 、WS 2 Etc. with suitable band gap (1-2 eV), the on-off ratio can reach 10 8 But its electron mobility is not high (values of only a few square centimeters per volt per second). In contrast, germanenes have very high carrier mobilities (10) 5 cm 2 V -1 s -1 ) Although it is still a zero band gap graphene-like two-dimensional material, its band gap can be further opened by hydrogenation. Research shows that the band gap of the hydrogermylene (germane) can reach 1.56eV, and the theoretical carrier mobility can reach 18000cm 2 V -1 s -1 The above. The doping and functionalization of germane can further adjust the band gap, thereby regulating the electronic property and the optical characteristic of germane. As early as 2001, vogg et al studied Si/Ge alloy two-dimensional bulk materials with band gaps that can vary from 1.3-2.4 eV. In 2014, arguilla et al prepared Sn doped germane, and the germane band gap was reduced from 1.59eV to 1.38eV as the doping amount of Sn was increased.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a two-dimensional layered tellurium-doped germane and a preparation method thereof.
The technical purpose of the invention is realized by the following technical scheme.
A two-dimensional layered tellurium-doped germane and a preparation method thereof are carried out according to the following steps: vacuum packaging Ge, geTe and Ca in a quartz tube according to the molar ratio of the precursor, placing in a vacuum tube furnace, setting a temperature control program, heating to 1000-1100 ℃ within 300 +/-20 min from room temperature, maintaining for melting, and cooling to obtain CaGe 2-2x Te 2x (x = 0.01-0.05), and then reacting the precursor with excessive hydrochloric acid at-35 to-45 ℃ to remove element calcium to obtain a two-dimensional layered semiconductor material tellurium-doped germane HGe 1-x Te x (x＝0.01-0.05)。
Furthermore, the room temperature is 20-30 ℃ in the temperature control program.
Furthermore, the vacuum degree in the vacuum tube furnace needs to be less than 0.1 MPa.
Furthermore, in the temperature control program, the temperature is maintained at 1000-1100 ℃ for 1000-1200 min for melting, and preferably at 1050-1100 ℃ for 1100-1200 min; cooling to room temperature at 5-10 deg.c/min.
Furthermore, the precursor is reacted with an excess of hydrochloric acid, with a stirring speed of 200 to 800r/min and a reaction time of 150 to 350 hours, preferably 200 to 300 hours.
And after the precursor reacts with excessive hydrochloric acid, the obtained product is respectively washed with deionized water and ethanol for three times, and vacuum drying is carried out for 6-8 h at the room temperature of 20-30 ℃ to obtain the two-dimensional layered semiconductor material tellurium-doped germane HGe 1-x Te x (x＝0.01-0.05)。
And when the precursor reacts with excessive hydrochloric acid, the amount of hydrochloric acid is excessive relative to the amount of calcium in the precursor, so as to completely remove the element calcium.
The technical scheme of the invention provides a two-dimensional layered tellurium-doped germane and a preparation method thereof, wherein Ca, geTe,And (3) packaging Ge in a tube furnace according to a certain stoichiometric ratio, performing program temperature control to obtain a precursor, and reacting the precursor with hydrochloric acid at a low temperature to obtain a two-dimensional layered semiconductor material tellurium-doped germane. GeTe is used as a germanium compound, has better solubility with Ge, has a two-dimensional structure, is beneficial to Ca entering the interlayer, and can ensure that the components are more uniform to obtain a better precursor CaGe 2-2x Te 2x (x = 0.01-0.05). Moreover, the doped germane can adjust the band gap, so that the doped germane has good electrical property and optical property and is worthy of further research. The two-dimensional material has great potential application in photoelectric devices, energy storage, photocatalysis and the like.
Drawings
FIG. 1 shows CaGe prepared by the technical scheme of the invention 2-2x Te 2x (x = 0.01-0.05) XRD spectrum pattern of precursor, wherein 1%, 3% and 5% correspond to mole percent Te/(Te + Ge) of Te in examples 1-3, respectively.
FIG. 2 shows a two-dimensional layered semiconductor material of tellurium doped germane HGe prepared by the technical scheme of the invention 1-x Te x (x = 0.01-0.05) XRD spectrum, where 1%, 3% and 5% correspond to the mole percentage Te/(Te + Ge) of Te in examples 1-3, respectively.
FIG. 3 shows a two-dimensional layered semiconductor material of tellurium doped germane HGe prepared by the technical scheme of the invention 1-x Te x SEM photographs (x = 0.01-0.05) in which 1%, 3% and 5% correspond to the mole percentage Te/(Te + Ge) of Te in examples 1-3, respectively.
FIG. 4 shows a two-dimensional layered semiconductor material of Te doped germane HGe prepared by the technical solution of the present invention 1-x Te x (x = 0.01-0.05) band gap vs. Te doping, where 1%, 3% and 5% correspond to the mole percent Te/(Te + Ge) of Te in examples 1-3, respectively.
Detailed Description
The present invention will be further described with reference to the following embodiments. Concentrated hydrochloric acid (aqueous solution of hydrogen chloride) is used, the mass percentage of which is 30-35 wt%.
Example 1
Glove boxWeighing 0.01mol Ca, 0.0196mol Ge and 0.2 mol GeTe in sequence, adding into a quartz tube in sequence, sealing by using a vacuum tube sealing system, sintering in a vacuum tube furnace, controlling the temperature for 300min, increasing the temperature from normal temperature to 1050 ℃, maintaining the temperature for 1200min, and cooling to normal temperature at the speed of 5 ℃/min. 1g of the precursor is taken to react with 150mL of hydrochloric acid at-35 ℃, and the mixture is stirred for 7 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 6h to obtain the two-dimensional layered semiconductor material tellurium-doped germane HGe 0.99 Te 0.01 。
Example 2
0.01mol of Ca, 0.0188mol of Ge and 0.6mol of GeTe are sequentially weighed in a glove box, sequentially added into a quartz tube, sealed by using a vacuum tube sealing system, sintered in a vacuum tube furnace, and controlled in temperature for 300min, increased from normal temperature to 1050 ℃, maintained for 1200min, and then cooled to normal temperature at the speed of 5 ℃/min. 1g of the precursor is taken to react with 150mL of hydrochloric acid at-35 ℃, and the mixture is stirred for 7 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 6h to obtain a two-dimensional layered semiconductor material of tellurium-doped germane HGe 0.97 Te 0.03 。
Example 3
0.01mol of Ca, 0.018mol of Ge and 1mmol of GeTe are sequentially weighed in a glove box, sequentially added into a quartz tube, sealed by a vacuum tube sealing system, sintered in a vacuum tube furnace, and subjected to temperature control procedures of raising the temperature from normal temperature to 1050 ℃ for 300min, maintaining the temperature for 1200min and then reducing the temperature to normal temperature at the rate of 5 ℃/min. 1g of the precursor is taken to react with 150mL of hydrochloric acid at-35 ℃, and the mixture is stirred for 7 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 6h to obtain a two-dimensional layered semiconductor material of tellurium-doped germane HGe 0.95 Te 0.05 。
Example 4
0.01mol of Ca, 0.018mol of Ge and 1mmol of GeTe are sequentially weighed in a glove box, sequentially added into a quartz tube, sealed by a vacuum tube sealing system, sintered in a vacuum tube furnace, and subjected to temperature control procedures of raising the temperature from normal temperature to 1050 ℃ for 300min, maintaining the temperature for 1200min and then reducing the temperature to normal temperature at the rate of 5 ℃/min. 1g of the precursor is taken to be mixed with 150mL of hydrochloric acid at the temperature of minus 35 DEG CThe reaction was continued and stirred for 9 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 6h to obtain the two-dimensional layered semiconductor material tellurium-doped germane HGe 0.95 Te 0.05 。
Example 5
0.01mol of Ca, 0.018mol of Ge and 1mmol of GeTe are sequentially weighed in a glove box, sequentially added into a quartz tube, sealed by a vacuum tube sealing system, sintered in a vacuum tube furnace, and subjected to temperature control procedures of raising the temperature from normal temperature to 1050 ℃ for 300min, maintaining the temperature for 1200min and then reducing the temperature to normal temperature at the rate of 5 ℃/min. 1g of the precursor is taken to react with 150mL of hydrochloric acid at-35 ℃, and stirred for 13 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum drying at room temperature for 6h to obtain the two-dimensional layered semiconductor material tellurium-doped germane HGe 0.95 Te 0.05 。
Example 6
0.01mol of Ca, 0.018mol of Ge and 1mmol of GeTe are sequentially weighed in a glove box, sequentially added into a quartz tube, sealed by a vacuum tube sealing system, sintered in a vacuum tube furnace, and subjected to temperature control procedures of raising the temperature from normal temperature to 1050 ℃ for 300min, maintaining the temperature for 1200min and then reducing the temperature to normal temperature at the rate of 5 ℃/min. 1g of the precursor is taken to react with 150mL of hydrochloric acid at-45 ℃, and the mixture is stirred for 7 days. Washing the obtained product with deionized water and ethanol for three times respectively, and vacuum-drying at room temperature for 6h to obtain a two-dimensional layered semiconductor material of tellurium-doped germane HGe 0.95 Te 0.05 。
As shown in attached figures 1 and 2, the technical scheme of the invention can be used for successfully preparing CaGe 2-2x Te 2x (x = 0.01-0.05) precursor and two-dimensional layered semiconductor material tellurium-doped germane HGe 1-x Te x (x = 0.01-0.05), the precursor and the two-dimensional layered material show substantially identical XRD characteristic lines with the change of Te element. And the appearance of the two-dimensional layered material is basically kept unchanged along with the change of Te element through SEM characterization. The band gap of the two-dimensional layered material is tested by using an ultraviolet detection method, as shown in figure 4, the band gap shows a descending trend along with the increase of Te element, and is reduced from 1.48-1.49 eV close to 1.50 to 1.16-1.17 eV below 1.20, namely the band gap can pass through the dosage of Te elementThe band gap of the two-dimensional layered material is adjusted in a variable manner.
According to the technical scheme of the invention, the preparation of the two-dimensional layered semiconductor material tellurium-doped germane can be realized by adjusting the process parameters, and the performance basically consistent with that of the invention is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (6)
1. The two-dimensional layered tellurium-doped germane is characterized by comprising the following steps of: vacuum packaging Ge, geTe and Ca in a quartz tube according to the molar ratio of the precursor, placing in a vacuum tube furnace, setting a temperature control program, heating to 1000-1100 ℃ within 300 +/-20 min from room temperature, maintaining for 1000-1200 min for melting, and cooling to obtain CaGe 2-2x Te 2x Precursor, wherein x =0.01-0.05, and cooling to room temperature at 5-10 ℃/min in cooling; then the precursor reacts with excessive hydrochloric acid at the temperature of minus 35 ℃ to minus 45 ℃ to remove element calcium, and a two-dimensional layered semiconductor material tellurium-doped germane HGe is obtained 1-x Te x Wherein x =0.01-0.05, the stirring speed is 200-800r/min, and the reaction time is 150-350 hours.
2. A two-dimensional layered tellurium-doped germane as claimed in claim 1, wherein the vacuum degree in the vacuum tube furnace is required to be below 0.1 MPa.
3. The two-dimensional layered tellurium-doped germane as claimed in claim 1, wherein the hydrochloric acid is concentrated hydrochloric acid with a mass percentage of 30-35 wt%.
4. A method for preparing two-dimensional layered tellurium-doped germane as claimed in claim 1, characterized by the following steps: vacuum packaging Ge, geTe and Ca three substances in a quartz tube according to the molar ratio of a precursor, and placing the three substances in vacuumSetting temperature control program in a tube furnace, heating to 1000-1100 ℃ within 300 +/-20 min from room temperature and maintaining for 1000-1200 min for melting, and cooling to obtain CaGe 2-2x Te 2x Precursor, wherein x =0.01-0.05, and the temperature is reduced to room temperature at 5-10 ℃/min in cooling; then the precursor reacts with excessive hydrochloric acid at the temperature of minus 35 to minus 45 ℃ to remove element calcium, and the two-dimensional layered semiconductor material tellurium-doped germane HGe is obtained 1-x Te x Wherein x =0.01-0.05, the stirring speed is 200-800r/min, and the reaction time is 150-350 hours.
5. The method according to claim 4, wherein the degree of vacuum in the vacuum tube furnace is less than 0.1 MPa.
6. The method according to claim 4, wherein the hydrochloric acid is concentrated hydrochloric acid with a mass percentage of 30-35 wt%.
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Citations (5)
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|---|---|---|---|---|
| DE1061302B (en) * | 1956-12-12 | 1959-07-16 | Kali Chemie Ag | Process for the preparation of hydrogen compounds of the elements of groups IV and V of the periodic table |
| CN104099578A (en) * | 2013-04-11 | 2014-10-15 | 气体产品与化学公司 | Method of making a multicomponent film |
| CN108330304A (en) * | 2018-01-24 | 2018-07-27 | 福州大学 | A kind of cubic phase Ca preparing Te doping using rapid solidification method2Ge |
| CN108726557A (en) * | 2017-04-24 | 2018-11-02 | 天津大学 | A kind of fluorination germanium hydrogen two-dimensional material and preparation method |
| CN110117744A (en) * | 2018-02-05 | 2019-08-13 | 天津大学 | A kind of hydroxylated two-dimensional semiconductor germanium-silicon alloy of hydrogenation-with gap tunable and preparation method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1061302B (en) * | 1956-12-12 | 1959-07-16 | Kali Chemie Ag | Process for the preparation of hydrogen compounds of the elements of groups IV and V of the periodic table |
| CN104099578A (en) * | 2013-04-11 | 2014-10-15 | 气体产品与化学公司 | Method of making a multicomponent film |
| CN108726557A (en) * | 2017-04-24 | 2018-11-02 | 天津大学 | A kind of fluorination germanium hydrogen two-dimensional material and preparation method |
| CN108330304A (en) * | 2018-01-24 | 2018-07-27 | 福州大学 | A kind of cubic phase Ca preparing Te doping using rapid solidification method2Ge |
| CN110117744A (en) * | 2018-02-05 | 2019-08-13 | 天津大学 | A kind of hydroxylated two-dimensional semiconductor germanium-silicon alloy of hydrogenation-with gap tunable and preparation method |
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