CN110746452A - Method for preparing high-performance material by methylating two-dimensional material CaGeTe - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000012761 high-performance material Substances 0.000 title claims abstract description 13
- 230000001035 methylating effect Effects 0.000 title claims abstract description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- 239000004809 Teflon Substances 0.000 claims abstract description 10
- 229920006362 Teflon® Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000011987 methylation Effects 0.000 claims abstract description 4
- 238000007069 methylation reaction Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 25
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 8
- 238000013021 overheating Methods 0.000 abstract description 8
- 238000005245 sintering Methods 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 229910005900 GeTe Inorganic materials 0.000 description 11
- 239000002356 single layer Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910005866 GeSe Inorganic materials 0.000 description 1
- 229910005742 Ge—C Inorganic materials 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- -1 comprises O Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
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- Crystals, And After-Treatments Of Crystals (AREA)
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Abstract
The invention discloses a method for preparing a high-performance material by methylating a two-dimensional material CaGeTe, which comprises the steps of controlling the temperature by a program in a CVD (chemical vapor deposition) tube furnace, sintering to obtain a CaGeTe precursor, sequentially washing with toluene and ethanol for multiple times, drying, adding a magnetic stirrer, deionized water, acetonitrile, the CaGeTe precursor and methyl iodide into a three-neck flask, ensuring that a rotor continuously rotates, and carrying out sealed and light-proof reaction to obtain GeTe-CH3. Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 2 hr to prevent overheating of bathtub and liquid, cooling with water at 20 deg.C, and centrifuging to obtain GeTe-CH two-dimensional layered semiconductor material3. Compared with CaGeTe, the two-dimensional material obtained after methylation has obviously improved optical band gap and has greater potential in the aspects of photoelectric devices, photocatalysis and the like.
Description
Technical Field
The invention belongs to the technical field of two-dimensional functional materials, and particularly relates to methylated GeTe-CH obtained by organic functionalization of a two-dimensional material CaGeTe3。
Background
Two-dimensional layered transition metal chalcogenide-TMDCs with a graphene-like structure are widely applied to the aspects of photodetectors, field effect transistors and the like based on excellent light absorption rate and easily-regulated optical band gaps, and are attracted by students. The two-dimensional IV group metal chalcogenide compound-GIVMCs (the metal mainly comprises Si, Ge and Sn, and the chalcogen mainly comprises O, S, Se and Te) with similar structure has optical performance suitable for photocatalysis (for example, the single-layer SnSe can reach 38 percent of light absorptivity found by Shi et al), excellent electrical performance (for example, the prior SnS-based metal chalcogenide compound-GIVMCs have excellent electrical performance2The carrier mobility of the prepared FET device reaches 230cm2 & V-1·s-1The on-off ratio is more 106) Moreover, due to the anisotropy of the crystal structure, the differences between the direct band gap and the indirect band gap of the SnS, SnSe, GeSe and the like are small, and the GIVMCs can be mutually converted under certain mechanical strength, and the like, so that the GIVMCs are widely researched in recent years. In 2018, Zhang et al experimentally peel off for the first time to obtain a layered GeTe material, the single-layer GeTe has an optical band gap of 1.93eV, and then Qiao et al theoretically calculate GeTe, and the single-layer GeTe has a band gap of 2.35eV, which is relatively consistent with the experiment, all of which show that the two-dimensional novel material GeTe has a proper band gap, so that the optical performance and the electrical performance of the material are worth further research, but because GeTe is difficult to functionalize, an effective means needs to be provided for the functionalization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a high-performance material by methylating a two-dimensional material CaGeTe, which starts with a ternary precursor CaGeTe, methylates the CaGeTe by methyl iodide to replace Ca by methyl to obtain the two-dimensional material GeTe-CH3Namely methylating CaGeTe to obtain the high-performance two-dimensional material.
The method for preparing the high-performance material by methylating the two-dimensional material CaGeTe comprises the following steps:
in step 1, the three metals are weighed according to the principle of the equimolar ratio of the three metals, and Te is selected to be slightly excessive so as to ensure that no excessive Ca and Ge exist in the reactant.
In step 1, a CVD tube furnace is selected for program temperature control.
In the step 1, the temperature is uniformly raised from room temperature of 20-25 ℃ to 1050-1100 ℃ within 350-400 min, the temperature is kept for 1200-1500 min, then the temperature is lowered to 800-850 ℃ within 1100-1200 min, and finally the temperature is slowly lowered to the room temperature of 20-25 ℃ at the speed of 0.1-0.5 ℃/min.
In step 1, after a CaGeTe precursor is obtained, the CaGeTe precursor is washed with toluene and ethanol for multiple times in sequence to remove excessive Te, and then dried.
In the step 2, the dosage of the deionized water is 10-20 parts by volume, and each part by volume is 1 ml; the using amount of acetonitrile is 1-5 parts by volume, and each part by volume is 1 ml; the dosage of the methyl iodide is 1-5 volume parts, and each volume part is 1 ml; the amount of the CaGeTe precursor is 50-100 parts by mass, and each part by mass is 1 mg.
In the step 2, the usage amount of the deionized water is 15-20 parts by volume, and each part by volume is 1 ml; the using amount of acetonitrile is 1-3 parts by volume, and each part by volume is 1 ml; the dosage of the methyl iodide is 3-5 volume parts, and each volume part is 1 ml; the amount of the CaGeTe precursor is 60-80 parts by mass, and each part by mass is 1 mg.
In step 2, the stirring is carried out by ultrasound, the rotation speed per minute is 100-500 revolutions, and the reaction time is 50-220 hours, preferably 100-200 hours.
In the step 3, the GeTe-OH layered material is obtained by centrifugation after ultrasonic stripping by a solution method, and the centrifugation rate is 3000-5000 rmp.
In step 3, sonication is carried out for 1 to 5 hours, preferably 2 to 4 hours.
In step 3, water cooling is used to maintain the system at a temperature of 20 ± 0.5 degrees celsius.
In the technical scheme of the invention, the temperature is controlled by a program in a CVD (chemical vapor deposition) tube furnace, a CaGeTe precursor is obtained by sintering, toluene and ethanol are sequentially used for washing for multiple times, a magnetic stirrer, deionized water, acetonitrile, the CaGeTe precursor and methyl iodide are added into a three-neck flask after drying, the rotor is ensured to rotate continuously, and GeTe-CH is obtained by sealing and reacting in a dark place3. Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 2 hr to prevent overheating of bathtub and liquid, cooling with water at 20 deg.C, and centrifuging to obtain GeTe-CH two-dimensional layered semiconductor material3. Compared with CaGeTe, the two-dimensional material obtained after methylation has obviously improved optical band gap and has greater potential in the aspects of photoelectric devices, photocatalysis and the like.
Description of the drawings:
FIG. 1 shows GeTe-CH prepared by the present invention3An infrared spectrum of (1).
FIG. 2 shows GeTe-CH prepared by the present invention3Scanning electron micrograph (c).
FIG. 3 shows GeTe and GeTe-CH prepared by the present invention3Ultraviolet-visible absorption spectrum of (a).
Detailed Description
The present invention will be further described with reference to the following embodiments. The following examples of the present invention are given to further illustrate the present invention, but not to limit the scope of the present invention.
Example 1
Weighing 10mmol Ca, 10mmol Ge and 11mmol Te in sequence in a glove box, vacuum sintering in a CVD tube furnace in 400min from normal temperature to 1050 deg.C, maintaining for 1200min, cooling to 800 deg.C in 1200min, slowly cooling to normal temperature at 0.5 deg.C/min,washing with toluene and ethanol in sequence, drying, adding a magnetic stirrer, 15ml of deionized water, 2ml of acetonitrile, 60mg of CaGeTe precursor and 3ml of methyl iodide into a three-neck flask, stirring, sealing and reacting for 72 hours in a dark place to obtain GeTe-CH3. Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 2 hr to avoid overheating of bathtub and liquid, cooling with water at 20 deg.C, centrifuging 3000rnp to obtain two-dimensional layered semiconductor material GeTe-CH3。
Example 2
Weighing 10mmol Ca, 10mmol Ge and 12mmol Te in sequence in a glove box, placing in a packaged quartz tube, vacuum sintering in a CVD tube furnace, heating to 1100 deg.C from normal temperature for 300min, maintaining for 1500min, cooling to 800 deg.C for 1200min, slowly cooling to normal temperature at 0.5 deg.C/min, washing with toluene and ethanol in sequence, drying, adding magnetic stirrer, 20ml deionized water, 5ml acetonitrile, 100mg CaGeTe precursor and 5ml ethyl iodide, stirring, sealing, and reacting in dark place for 100 hr to obtain GeTe-CH3. Adding GeTe-CH3Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 1 hr to prevent overheating of bathtub and liquid, cooling with water at 20 deg.C, centrifuging 3000rnp to obtain two-dimensional layered semiconductor material GeTe-CH3。
Example 3
Weighing 10 mmole Ca, 10 mmole Ge and 11 mmole Te in turn in a glove box, placing the weighed materials into a packaged quartz tube, sintering the materials in a CVD tube furnace in vacuum for 350min, heating the materials to 1000 ℃ from normal temperature, maintaining the temperature for 1200min, cooling the materials to 900 ℃ for 1000min, then slowly cooling the materials to the normal temperature at 0.3 ℃/min, washing the materials with methylbenzene and ethanol in turn, adding a magnetic stirrer, 15ml deionized water, 3ml acetonitrile, 60mg CaGeTe precursor and 2ml 1-iodopropane into a three-neck flask after drying, stirring, sealing and reacting the materials in a dark place for 150 hours to obtain GeTe-CH3. Adding GeTe-CH3Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 5 hr to prevent overheating of bathtub and liquid, cooling with water at 20 deg.C, centrifuging 5000rnp to obtain two-dimensional layered semiconductor material GeTe-CH3。
Example 4
Weighing in sequence in glove box10mmolCa, 10mmolGe and 11mmolTe, a quartz tube is packaged, a CVD tube furnace is used for vacuum sintering, the temperature is increased to 1200 ℃ from the normal temperature within 400min, the temperature is reduced to 800 ℃ within 1100min after the temperature is maintained for 1200min, then the temperature is slowly reduced to the normal temperature at 0.1 ℃/min, toluene and ethanol are used for washing in sequence, a magnetic stirrer, 10ml deionized water, 1ml acetonitrile, 50mg CaGeTe precursor and 1ml methyl iodide are added into a three-mouth flask after drying, stirring, sealing and light-shielding reaction are carried out for 120 hours, and GeTe-CH is obtained3. Adding GeTe-CH3Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 3 hr to avoid overheating of bathtub and liquid, cooling with water at 20 deg.C, centrifuging 5000rnp to obtain two-dimensional layered semiconductor material GeTe-CH3。
Example 5
Weighing 10mmol Ca, 10mmol Ge and 12mmol Te in turn in a glove box, placing in a packaged quartz tube, vacuum sintering in a CVD tube furnace, heating to 1050 ℃ from normal temperature for 300min, maintaining for 1200min, cooling to 850 ℃ for 1200min, slowly cooling to normal temperature at 0.5 ℃/min, washing with toluene and ethanol in turn, drying, adding a magnetic stirrer, 10ml deionized water, 4ml acetonitrile, 80mg CaGeTe precursor and 5ml methyl iodide, stirring, sealing and reacting in dark place for 200 hours to obtain GeTe-CH3. Adding GeTe-CH3Dispersing in a small bottle filled with ethanol, sealing the bottle with Teflon tape, ultrasonic treating for 4 hr to prevent overheating of bathtub and liquid, cooling with water at 20 deg.C, centrifuging at 4000rnp to obtain GeTe-CH two-dimensional layered semiconductor material3。
Example 6
Weighing 10 mmole Ca, 10 mmole Ge and 11 mmole Te in turn in a glove box, placing the weighed materials into a packaged quartz tube, sintering the materials in a CVD tube furnace in vacuum for 400min, heating the materials to 1050 ℃ from normal temperature, maintaining the temperature for 1000min, cooling the materials to 800 ℃ for 1000min, then slowly cooling the materials to the normal temperature at 0.5 ℃/min, washing the materials with methylbenzene and ethanol in turn, adding a magnetic stirrer, 15ml deionized water, 3ml acetonitrile, 60mg CaGeTe precursor and 3ml methyl iodide into a three-neck flask after drying, stirring, sealing and reacting the materials in a dark place for 220 hours to obtain GeTe-CH3. Adding GeTe-CH3Dispersing in ethanol-containing vial, sealing the bottle with Teflon tape, and ultrasonic treating for 2 hr to avoid bathtub and liquidThe two-dimensional layered semiconductor material GeTe-CH can be obtained by overheating the body, maintaining the water cooling at 20 ℃, and centrifuging by 4000rnp3。
As shown in attached figures 1-3, the technical scheme of the invention is adopted to successfully prepare the two-dimensional layered semiconductor material GeTe-CH3Prepared GeTe-CH3Has a two-dimensional layered structure and shows infrared characteristic peaks of C-H and Ge-C. Bulk GeTe and GeTe-CH without any treatment (i.e., ultrasonic centrifugal stripping) using optical band gap measurements of different numbers of layers in UV-visible absorption spectroscopy3Almost no band gap, bulk GeTe of 0.1eV, bulk GeTe-CH30.76eV, gradually decreasing the number of layers, gradually increasing the band gap, increasing the centrifugal rate, obtaining single-layer GeTe and GeTe-CH3The single layer GeTe is 1.86eV, and the single layer GeTe-CH3Is 2.12eV (band gap).
The process parameters are adjusted according to the content of the invention, and the two-dimensional layered semiconductor material GeTe-CH can be realized3And exhibit substantially the same properties as the examples. 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 (8)
1. The method for preparing the high-performance material by methylating the two-dimensional material CaGeTe is characterized by comprising the following steps of:
step 1, according to the molar ratio of Ca, Ge and Te of 1: 1: (1-1.2) weighing three metals of Ca, Ge and Te, uniformly mixing, uniformly heating to 1000-1200 ℃ from 20-25 ℃ in 300-400 min, keeping the temperature for 1000-1500 min, cooling to 800-900 ℃ in 1000-1200 min, and finally slowly cooling to 20-25 ℃ at 0.1-0.5 ℃/min to obtain a CaGeTe precursor;
step 2, adding deionized water, acetonitrile, CaGeTe precursor and methyl iodide into a reaction container, sealing and reacting at room temperature of 20-25 ℃ in the dark under the stirring condition to obtain GeTe-CH3Removing fromThe using amount of the sub-water is 10-20 parts by volume, and each part by volume is 1 ml; the using amount of acetonitrile is 1-5 parts by volume, and each part by volume is 1 ml; the dosage of the methyl iodide is 1-5 volume parts, and each volume part is 1 ml; the amount of the CaGeTe precursor is 50-100 parts by mass, and each part by mass is 1 mg;
step 3, adding GeTe-CH3Dispersing in a reaction container filled with ethanol, sealing the bottle mouth with Teflon tape, performing ultrasonic treatment, maintaining the temperature of the system at 20-25 deg.C, and centrifuging to obtain two-dimensional layered semiconductor material GeTe-CH3。
2. The method for preparing high-performance material by methylation of two-dimensional material CaGeTe according to claim 1, wherein in step 1, the molar ratio of three metals is equal when the three metals are weighed, and Te is selected to be slightly excessive so as to ensure that no excess Ca and Ge exist in the reactant.
3. The method for preparing the high-performance material by methylating the two-dimensional material CaGeTe according to claim 1, wherein in the step 1, a CVD tube furnace is selected for program temperature control, the temperature is raised from room temperature of 20-25 ℃ to 1050-1100 ℃ at a constant speed within 350-400 min, the temperature is kept for 1200-1500 min, then the temperature is reduced to 800-850 ℃ within 1100-1200 min, and finally the temperature is slowly reduced to the room temperature of 20-25 ℃ at the speed of 0.1-0.5 ℃/min.
4. The method for preparing the high-performance material by methylating the two-dimensional material CaGeTe according to claim 1, wherein in the step 2, the amount of the deionized water is 15-20 parts by volume, and each part by volume is 1 ml; the using amount of acetonitrile is 1-3 parts by volume, and each part by volume is 1 ml; the dosage of the methyl iodide is 3-5 volume parts, and each volume part is 1 ml; the amount of the CaGeTe precursor is 60-80 parts by mass, and each part by mass is 1 mg.
5. The method for preparing high-performance material by methylating CaGeTe as claimed in claim 1, wherein in step 2, ultrasonic agitation is used, the rotation speed per minute is 100-500 rpm, and the reaction time is 50-220 hours, preferably 100-200 hours.
6. The method for preparing the high-performance material by methylating the two-dimensional material CaGeTe according to claim 1, wherein in the step 3, the GeTe-OH layered material is obtained by centrifuging after ultrasonic stripping by a solution method, and the centrifugation rate is 3000-5000 rmp.
7. The method for preparing high-performance material by methylation of two-dimensional material CaGeTe according to claim 1, wherein in step 3, the ultrasonic treatment is performed for 1-5 hours, preferably for 2-4 hours.
8. The method for preparing the high-performance material by methylating CaGeTe as claimed in claim 1, wherein in step 3, water cooling is used to maintain the temperature of the system at 20 +/-0.5 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187240A (en) * | 1977-10-13 | 1980-02-05 | Eastman Kodak Company | Process for preparing tellurium(II) materials |
| US5652037A (en) * | 1993-09-22 | 1997-07-29 | Kabushiki Kaisha Toshiba | Information recording medium |
| US20030151117A1 (en) * | 2000-03-26 | 2003-08-14 | Gunther Vogg | Semiconductor polymers, method for the production thereof and an optoelectronic component |
| US20170200906A1 (en) * | 2013-04-22 | 2017-07-13 | Ohio State Innovation Foundation | Germanane analogs and optoelectronic devices using the same |
| CN107814571A (en) * | 2017-11-01 | 2018-03-20 | 上海出入境检验检疫局工业品与原材料检测技术中心 | A kind of SnTe nano composite materials and its preparation method and application |
-
2018
- 2018-07-24 CN CN201810821805.0A patent/CN110746452A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187240A (en) * | 1977-10-13 | 1980-02-05 | Eastman Kodak Company | Process for preparing tellurium(II) materials |
| US5652037A (en) * | 1993-09-22 | 1997-07-29 | Kabushiki Kaisha Toshiba | Information recording medium |
| US20030151117A1 (en) * | 2000-03-26 | 2003-08-14 | Gunther Vogg | Semiconductor polymers, method for the production thereof and an optoelectronic component |
| US20170200906A1 (en) * | 2013-04-22 | 2017-07-13 | Ohio State Innovation Foundation | Germanane analogs and optoelectronic devices using the same |
| CN107814571A (en) * | 2017-11-01 | 2018-03-20 | 上海出入境检验检疫局工业品与原材料检测技术中心 | A kind of SnTe nano composite materials and its preparation method and application |
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Application publication date: 20200204 |
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