CN108217732A - 一种纤锌矿cmts纳米晶的制备方法 - Google Patents
一种纤锌矿cmts纳米晶的制备方法 Download PDFInfo
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- 229910000238 buergerite Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 34
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000010792 warming Methods 0.000 claims abstract description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003599 detergent Substances 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- SQEDZTDNVYVPQL-UHFFFAOYSA-N dodecylbenzene;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1 SQEDZTDNVYVPQL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 229940094933 n-dodecane Drugs 0.000 claims description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical group CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 2
- 235000010234 sodium benzoate Nutrition 0.000 claims description 2
- 239000004299 sodium benzoate Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims 1
- 229940093474 manganese carbonate Drugs 0.000 claims 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- BIMRNYDJQHZYKY-UHFFFAOYSA-N CCCCCCCCCCCC.[S] Chemical compound CCCCCCCCCCCC.[S] BIMRNYDJQHZYKY-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- SDPBZSAJSUJVAT-UHFFFAOYSA-N carbonic acid;manganese Chemical compound [Mn].OC(O)=O SDPBZSAJSUJVAT-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- -1 rare earth Chalcogenide Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种纤锌矿CMTS纳米晶的制备方法,属于光伏材料与器件新能源技术领域。本发明将铜源、锰源、锡源、十二烷基苯酸钠加入到有机溶剂中并溶解,然后匀速升温至温度为100~120℃得到前躯体溶液;在前躯体溶液中依次加入正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为140~180℃反应15~60min,再匀速升温至250~300℃反应30~60min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗3~5次固体,干燥即得纤锌矿Cu2MnSnS4纳米晶。本发明方法制得的纤锌矿Cu2MnSnS4纳米晶产量大,产率高,纳米晶原子比例易于调控,纤锌矿Cu2MnSnS4纳米晶的平均粒径为纳米级。
Description
技术领域
本发明涉及一种纤锌矿CMTS纳米晶的制备方法,属于光伏材料与器件新能源技术领域。
背景技术
近年来,能源危机和环境污染迫使人们开发绿色高效的技术。硫化物材料如CuInSe,Cu2InGa(Se,S)4,CdTe,Bi2Te3,PbTe等已经被广泛应用于光电,光催化和热电领域。然而,由于铟(In)和碲(Te)的稀有性和镉(Cd)的毒性的限制,对开发稀土,廉价和环境友好的硫族化物材料的关注越来越多。作为新型能量转换材料,Cu2ZnSnS4(CZTS)在研究人员中非常受欢迎。 Cu2MnSnS4(CMTS)由于其与CZTS的结构类似,因此也被认为是可能的能量转换材料。在过去几年中,科学家们研究了CMTS的光学,铁电和磁电性质。还通过热注入,微波照射,浸涂,静电纺丝等各种方法合成了CMTS化合物,在RSC Advances, 2012, 2, 5044-5046这篇文章中,作者采用热注入的方法制备CMTS粉末,然而其工艺复杂,制得的粉末直径偏大且不均匀,这是由于加热设备控温不准确导致,在J. Mater. Chem., 2012, 22, 23136这篇文章中,作者通过使用溶剂热的方法制备样品,试验时间很长,且设备冗杂,同样有温度不易控制的缺陷,使得到的粉末性质也一般。
发明内容
本发明针对现有技术的不足,提供一种纤锌矿CMTS纳米晶的制备方法,本发明方法具有工艺简单、反应条件温和、时间短、环境友好、制备过程直观可控的特点,本发明方法的单次产量比现有制备方法提高一个数量级,有利于大规模生产。本发明制备的Cu2MnSnS4纳米晶可作为太阳能电池的吸收层材料,且Cu2MnSnS4纳米晶中包含的元素皆是无毒的,具有很高的光吸收系数,为直接带隙半导体材料,带隙大约在1.2~1.4eV,粒径均匀,光学性质良好。
一种纤锌矿CMTS纳米晶的制备方法,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为(1.4~2):1:(0.6~1)的比例,将铜源、锰源、锡源、十二烷基苯酸钠加入到有机溶剂中并溶解,然后置于油浴中匀速升温至温度为100~120℃得到前躯体溶液,其中有机溶剂为油胺、油酸或十八胺;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为140~180℃反应15~60min,再匀速升温至250~300℃反应30 ~60min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗3~5次固体,干燥即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:(2~4),有机洗涤液为正己烷、甲醇和乙醇的有机混合液;
所述步骤(1)前躯体溶液中十二烷基苯酸钠与锰源的摩尔比为(1~1.8):1;
所述步骤(1)中铜源为碘化亚铜、氯化亚铜或硫酸亚铜,锰源为醋酸锰、硫酸锰或碳酸锰,锡源为氯化锡、碘化锡或二硫化锡;
所述步骤(2)中正己烷、甲醇、乙醇的体积比为(1~1.5):(1~2):1;
所述步骤(2)中干燥温度为60~80℃,干燥时间为8~12h。
本发明中,以油胺、油酸或十八胺与正十二烷硫醇混合液作为溶剂,可以通过改变前驱体配比例、体系反应时间及温度等反应条件以保证较高的成核速率、良好的粒子尺寸分布以及形貌。
本发明的有益效果:
(1)本发明方法中原料均为常见化学药品(金属碘盐、金属盐、二硫化碳、正十二烷硫醇、油胺),其成本低,产物质量好;
(2)本发明方法控温准确,温差为可控制在±0.1℃,能够有效控制成核,从而得到良好的粒子尺寸分布以及形貌、组分的纤锌矿Cu2MnSnS4;
(3)本发明方法制备的CMTS微粒产物具有的原子比例,微粒平均粒径为5~10 nm,粒径分布均匀;
(4)本发明所述方法产量大,产率高,Cu2MnSnS4纳米晶的单次产量比现有方法高一个数量级;
(5)本发明所述方法具有操作简单,制备过程直观可控,设备要求低等优点;制备出CMTS微粒结晶性好、可见光区域具有很好的吸收,有利于提高光电转换效率。
附图说明
图1为实施例1制备的Cu2MnSnS4纳米晶的XRD图;
图2为实施例1制备的Cu2MnSnS4纳米晶的TEM图;
图3为实施例1制备的Cu2MnSnS4纳米晶的EDX图;
图4为实施例1制备的Cu2MnSnS4纳米晶的UV-Vis图。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:一种纤锌矿CMTS纳米晶的制备方法,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为1.4:1:0.6的比例,将14mmol碘化亚铜、10mmol四水合醋酸锰、6mmol五水合氯化锡、10mmol十二烷基苯酸钠加入到48mL有机溶剂(有机溶剂为油胺)中并溶解,然后置于油浴中匀速升温至温度为100℃得到前躯体溶液;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入16mL正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为140℃反应60min,再匀速升温至250℃反应60 min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗3次固体,置于温度为60℃条件下干燥12h即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:2,搅拌速度为500rpm,有机洗涤液为正己烷、甲醇和乙醇的有机混合液,正己烷、甲醇、乙醇的体积比为1:1:1;
本实施例制备得到的纤锌矿Cu2MnSnS4纳米晶的XRD图如图1所示,从图1中可知,纤锌矿CMTS纳米晶的结晶性良好,无其它杂相;本实施例制备得到的纤锌矿Cu2MnSnS4纳米晶的TEM图如图2所示,从图2可知,纤锌矿CMTS纳米晶的粒径尺寸为5~10nm,粒径均匀;本实施例制备得到的纤锌矿Cu2MnSnS4纳米晶的EDX图如图3所示,纤锌矿CMTS纳米晶的元素原子计量比约为2:1:1:4,符合纤锌矿Cu2MnSnS4纳米晶的化学计量比,表明本实施例得到的纤锌矿Cu2MnSnS4纳米晶十分纯净;本实施例制备得到的纤锌矿Cu2MnSnS4纳米晶的UV-Vis图如图4所示,从图4中可知,CMTS的带隙在1.35eV,光学性能良好,可用以制备薄膜太阳能电池吸收层。
实施例2:一种纤锌矿CMTS纳米晶的制备方法,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为1.8:1:0.8的比例,将18mmol氯化亚铜、10mmol四水合醋酸锰、8mmol五水合碘化锡、15mmol十二烷基苯酸钠加入到有48mL机溶剂(有机溶剂为油酸)中并溶解,然后置于油浴中匀速升温至温度为120℃得到前躯体溶液;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入16mL正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为160℃反应30min,再匀速升温至280℃反应40 min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗4次固体,置于温度为60℃条件下干燥12h即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:3,搅拌速度为600rpm,有机洗涤液为正己烷、甲醇和乙醇的有机混合液,正己烷、甲醇、乙醇的体积比为1:1.5:1。
实施例3:一种纤锌矿CMTS纳米晶的制备方法,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为2:1:1的比例,将20mmol碘化亚铜、10mmol硫酸锰、10mmol二硫化锡、18mmol十二烷基苯酸钠加入到有48mL机溶剂(有机溶剂为油胺)中并溶解,然后置于油浴中匀速升温至温度为110℃得到前躯体溶液;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入16mL正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为180℃反应15min,再匀速升温至300℃反应30 min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗4次固体,置于温度为60℃条件下干燥12h即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:4,搅拌速度为500rpm,有机洗涤液为正己烷、甲醇和乙醇的有机混合液,正己烷、甲醇、乙醇的体积比为1.2:2:1。
实施例4:一种纤锌矿CMTS纳米晶的制备方法,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为2:1:1的比例,将20mmol硫酸亚铜、10mmol碳酸锰、10mmol二硫化锡、18mmol十二烷基苯酸钠加入到有48mL机溶剂(有机溶剂为十八胺)中并溶解,然后置于油浴中匀速升温至温度为120℃得到前躯体溶液;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入16mL正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为150℃反应50min,再匀速升温至280℃反应40min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗5次固体,置于温度为60℃条件下干燥12h即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:4,搅拌速度为500rpm,有机洗涤液为正己烷、甲醇和乙醇的有机混合液,正己烷、甲醇、乙醇的体积比为1.5:2:1。
Claims (4)
1.一种纤锌矿CMTS纳米晶的制备方法,其特征在于,具体步骤如下:
(1)按铜源、锰源、锡源的摩尔比为(1.4~2):1:(0.6~1)的比例,将铜源、锰源、锡源、十二烷基苯酸钠加入到有机溶剂中并溶解,然后置于油浴中匀速升温至温度为100~120℃得到前躯体溶液,其中有机溶剂为油胺、油酸或十八胺;
(2)在搅拌条件下,在步骤(1)所得前躯体溶液中依次加入正十二烷硫醇、二硫化碳混合均匀,匀速升温至温度为140~180℃反应15~60min,再匀速升温至250~300℃反应30 ~60min得到反应体系,冷却至室温,离心分离固液,采用有机洗涤液清洗3~5次固体,干燥即得纤锌矿Cu2MnSnS4纳米晶;其中正十二烷硫醇与有机溶剂的体积比为1:3,锰源与二硫化碳摩尔比为1:(2~4),有机洗涤液为正己烷、甲醇和乙醇的有机混合液。
2.根据权利要求1所述纤锌矿CMTS纳米晶的制备方法,其特征在于:步骤(1)前躯体溶液中十二烷基苯酸钠与锰源的摩尔比为(1~1.8):1。
3.根据权利要求1所述纤锌矿CMTS纳米晶的制备方法,其特征在于:步骤(1)中铜源为碘化亚铜、氯化亚铜或硫酸亚铜,锰源为醋酸锰、硫酸锰或碳酸锰,锡源为氯化锡、碘化锡或二硫化锡。
4.根据权利要求1所述纤锌矿CMTS纳米晶的制备方法,其特征在于:步骤(2)中正己烷、甲醇、乙醇的体积比为(1~1.5):(1~2):1。
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CN115385382A (zh) * | 2022-08-31 | 2022-11-25 | 上海电子信息职业技术学院 | 一种Ag、Fe共取代铜锌锡硫纳米晶的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105060338A (zh) * | 2015-07-29 | 2015-11-18 | 武汉理工大学 | 一种相选择性铜锌锡硫纳米晶的制备方法 |
CN106395886A (zh) * | 2016-09-13 | 2017-02-15 | 昆明理工大学 | 一种纤锌矿Cu2ZnSnS4纳米晶的大规模制备方法 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105060338A (zh) * | 2015-07-29 | 2015-11-18 | 武汉理工大学 | 一种相选择性铜锌锡硫纳米晶的制备方法 |
CN106395886A (zh) * | 2016-09-13 | 2017-02-15 | 昆明理工大学 | 一种纤锌矿Cu2ZnSnS4纳米晶的大规模制备方法 |
Non-Patent Citations (2)
Title |
---|
HAO GUAN ET AL.: "Photocatalytic and thermoelectric properties of Cu2MnSnS4 nanoparticles synthesized via solvothermal method", 《MATERIALS LETTERS》 * |
XIAOLU LIANG ET AL.: "Dilute Magnetic Semiconductor Cu2MnSnS4 Nanocrystals with a Novel Zincblende and Wurtzite Structure", 《RSC ADVANCES》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114566391A (zh) * | 2022-03-26 | 2022-05-31 | 安徽工程大学 | 一种超级电容器电极材料用过渡金属硫化物的制备方法 |
CN115385382A (zh) * | 2022-08-31 | 2022-11-25 | 上海电子信息职业技术学院 | 一种Ag、Fe共取代铜锌锡硫纳米晶的制备方法 |
CN115385382B (zh) * | 2022-08-31 | 2024-02-20 | 上海电子信息职业技术学院 | 一种Ag、Fe共取代铜锌锡硫纳米晶的制备方法 |
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