TW201631120A - 具有增進的穩定性及發光效率之量子點奈米粒子 - Google Patents
具有增進的穩定性及發光效率之量子點奈米粒子 Download PDFInfo
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- TW201631120A TW201631120A TW105116320A TW105116320A TW201631120A TW 201631120 A TW201631120 A TW 201631120A TW 105116320 A TW105116320 A TW 105116320A TW 105116320 A TW105116320 A TW 105116320A TW 201631120 A TW201631120 A TW 201631120A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 61
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 238000004020 luminiscence type Methods 0.000 title description 5
- 239000003446 ligand Substances 0.000 claims abstract description 56
- 125000000524 functional group Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 claims 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 abstract description 8
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- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 13
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- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 7
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- -1 cadmium chalcogenide Chemical class 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
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- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 5
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 4
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
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- VVGIYYKRAMHVLU-UHFFFAOYSA-N newbouldiamide Natural products CCCCCCCCCCCCCCCCCCCC(O)C(O)C(O)C(CO)NC(=O)CCCCCCCCCCCCCCCCC VVGIYYKRAMHVLU-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical class 0.000 description 2
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CRJGESKKUOMBCT-VQTJNVASSA-N N-acetylsphinganine Chemical compound CCCCCCCCCCCCCCC[C@@H](O)[C@H](CO)NC(C)=O CRJGESKKUOMBCT-VQTJNVASSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
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- 125000001549 ceramide group Chemical group 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
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- ZDVNRCXYPSVYNN-UHFFFAOYSA-K di(tetradecanoyloxy)indiganyl tetradecanoate Chemical compound [In+3].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O ZDVNRCXYPSVYNN-UHFFFAOYSA-K 0.000 description 1
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- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MIHRVCSSMAGKNH-UHFFFAOYSA-M n-ethylcarbamodithioate Chemical compound CCNC([S-])=S MIHRVCSSMAGKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HSSGIFXUHZEEEO-UHFFFAOYSA-N tris(methylsulfonyl)phosphane Chemical compound CS(=O)(=O)P(S(C)(=O)=O)S(C)(=O)=O HSSGIFXUHZEEEO-UHFFFAOYSA-N 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- WPZFNRZRCODGMX-UHFFFAOYSA-L zinc;ethoxymethanedithioate Chemical compound [Zn+2].CCOC([S-])=S.CCOC([S-])=S WPZFNRZRCODGMX-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/701—Chalcogenides
- C09K11/703—Chalcogenides with zinc or cadmium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
- H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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Abstract
本發明已發現特定二硫化合物係量子點(QD)奈米粒子之優異封蓋配位體。實例二硫配位體包含二硫代胺基甲酸鹽配位體。此等強結合配位體有能力配位至該奈米粒子表面之陽性及陰性原子。該等配位體係雙配位基及因此其對該QD表面之接近不似單配位基配位體接近般受空間位阻。此等配位體由此可完全使該QD表面飽和。
Description
本申請案主張2014年2月7日申請之美國臨時申請案第61/937,073號之權利。
不適用
本發明一般係關於半導體奈米粒子(「量子點」)。更特定而言,其係關於在其外表面具有封蓋配位體之半導體奈米粒子。
包含37 CFR1.97及1.98揭示資訊之先前技術描述
在製備及表徵2至100nm級尺寸之化合物半導體粒子(通常指量子點(QD)及/或奈米晶體)方面有受到大量關注。這主要由於其尺寸可調諧之電子、光學及化學性質。例如,眾多QD在電磁光譜之可見區域顯示強發射性。此外,吸收及發射光之波長係QD尺寸之函數。由於其獨特的光學性質,QD係多種商業應用之有前景材料,例如在眾多新穎及新興應用中之生物標記、太陽能電池、催化、生物成像、發光二極體。
迄今為止,最多研究及製備之半導體材料係II-VI族材料,即,ZnS、ZnSe、CdS、CdSe、CdTe,最顯著係CdSe,由於其在光譜可見
區域之可調諧性。如所提及之半導體奈米粒子由於其性質係受學術及商業關注,其係不同於相同半導體材料之相應結晶塊體形式之性質。兩個基頻因素,均與個別奈米粒子之尺寸有關,係代表其獨特性質。第一者係大表面對體積比。由於粒子變更小,表面原子數對在內部之彼等原子數比例增加。這導致表面性質在小粒子全部性質中起重要作用。利用半導體奈米粒子,第二因素係具有該粒度之材料的電子性質改變。特定而言,由於粒度減小能帶間隙逐漸變寬。能帶間隙之此改變係由於量子限域效應。此效應係「盒中電子」限域之結果,引起離散能階相似於在原子及分子中觀察之彼等,而不是相應塊體半導體材料之連續能帶。由此,對於半導體奈米粒子而言,由光子吸收產生之「電子及電洞」與該相應宏晶材料相比更加緊密在一起,導致在電子與電洞間不可忽視之庫倫力相互作用。這導致取決於粒度及組成之狹窄帶寬發射。因此,量子點與相應宏晶材料相比具有較高動態能量及第一激子轉變(能帶間隙)能量增長,同時粒子直徑減小。由此,具有較小直徑之量子點與具有較大直徑之量子點相比吸收及發射較高能量光。換言之,吸收及發射之光顏色作為粒子直徑之函數係可「調諧」。
單一核奈米粒子(其由單一半導體材料組成)趨向具有較低量子效率,由於發生位於該奈米粒子表面上會導致非輻射電子電洞復合之缺陷及懸掛鍵處的電子電洞復合。一種消除缺陷及懸掛鍵之方法係在核粒子表面生長具有更寬能帶間隙之第二半導體材料殼以產生「核殼粒子」。殼半導體材料較佳地具有與核材料失配之小晶格,使得在兩材料間之界面最小化。核殼粒子從表面狀態分離在核中受限制之電荷載波,否則其將作為非輻射復合中心。一常見實例係生長在CdSe核表面之ZnS。過度應變可進一步導致產生低量子效率之缺陷及非輻射電子電洞復合。
已經報導數個用於製備半導體奈米粒子之合成方法。早期途徑應用習知膠態之水性化學品,而更新近方法涉及使用有機金屬化合物動態控制奈米晶體沉澱。
由於QD之光學性質係尺寸依賴性,通常期望生產具有高度單分散性之QD群體,即,具有在該群中QD尺寸之高度均一性。亦期望具有高量子產率(QY,發射光子與吸收光子之比)之QD群體。已報道產生具有高度單分散性及具有大於50%量子產率之半導體QD的方法。大多數此等方法係基於由Murray、Norris及Bawendi在M.G.J.Am.Chem.Soc.1993,115,8706中描述之原始「成核及生長(nucleation and growth)」方法。Murray等人起初使用金屬-烷基(R2M)M=Cd、Zn、Te;R=Me、Et之有機金屬溶液及溶解於三正辛基膦(TOP)之三正辛基硫/硒化膦(TOPS/Se)。將此等前驅體溶液在120至400℃之溫度範圍時注入熱三正辛基氧化膦(TOPO)。這生產塗覆/覆蓋II-VI族材料半導體奈米粒子之TOPO。該粒子之尺寸可藉由溫度、所使用前驅體之濃度、及合成時間長度控制。此有機金屬途徑具有優於其他合成方法之優點,包含接近單分散性及高粒子結晶度。
鎘及用於習知QD之其他受限重金屬係高毒性及在商業應用中代表一個主要問題。含鎘QD之固有毒性阻止其用於包括動物或人類之任何應用。例如,新近研究提出由除非經保護,否則鎘硫屬化物半導體材料製造之QD在生物環境中係具細胞毒性。特定而言,經由各種途徑氧化或化學浸蝕可導致在該QD表面形成鎘離子,其可釋放至周圍環境。雖然表面塗層諸如ZnS可顯著降低該毒性,但不能完全消除它,由於QD可長時間在細胞中滯留或在人體中積累,在此期間其塗層可經歷一些暴露該富鎘核之降解。
毒性亦影響包含光電及通訊之應用,由於基於重金屬之材料在包括家庭電器諸如IT及通訊設備、照明設備、電及電子工具、玩具、
休閒及運動設備之眾多商業產品中普及。限制或禁止在商業產品中特定重金屬之法規已經在世界眾多地區實施。例如,歐盟指令2002/95/EC,熟知為「限制危險物質在電子設備中之使用(Restrictions on the use of Hazardous Substances in electronic equipment)」(或RoHS),禁止銷售包含高於特定含量之鉛、鎘、汞、六價鉻連同多溴化聯苯(PBB)及多溴化聯苯醚(PBDE)阻燃劑之新穎電及電子設備。由於此命令,製造商不得不尋找替代材料及開發用於創造普通電子設備之新穎製造方法。此外,在2007年6月1日,歐盟法規推動相關化學品及其安全使用(EC1907/2006)。該法規處理化學物質之登記、評估、授權及限制(Registration,Evaluation,Authorization and Restriction of Chemical substances)及熟知為「REACH」。該REACH法規強加給工業更大責任以管理化學品之風險及提供此等物質之安全資訊。預期相似法規將在世界範圍擴展開。由此,開發II-VI族QD材料之替代物具有極大經濟誘惑。
由於其提升之共價屬性,III-V族及IV-VI族高度結晶半導體奈米粒子更難於製備及一般需要更長退火時間。然而,現在有以II-VI族材料使用之相似方式製備之III-VI族及IV-VI族材料的報導。此等III-VI族及IV-VI族材料之實例包括GaN、Gap、GaAs、InP、InAs及用於PbS及PbSe。
對於全部上文之方法,快速粒子成核接著緩慢粒子生長對於狹窄粒度分佈係關鍵。全部此等合成方法係基於由Murray等人之原始有機金屬「成核及生長」方法,其包括快速將前驅體注入路易士鹼配位溶劑(封蓋劑)之熱溶液。冷卻劑溶液之添加降低反應溫度及輔助粒子生長但抑制進一步成核。隨後維持該溫度一段時間,其中所得粒子之尺寸取決於反應時間、溫度、及所用封蓋劑與前驅體之比。冷卻所得溶液,接著添加過量極性溶劑(甲醇或乙醇或有時丙酮)以產生可藉由
過濾或離心單離之粒子之沉澱物。一般而言,較大粒子與較小粒子相比更容易沉澱。由此,沉澱提供一種依照彼等尺寸分離量子點的方式。需要多個沉澱步驟以達成狹窄粒度分佈。
基本上,此等先前技術製法依賴粒子成核接著生長之原理。該原理依賴奈米粒子成核步驟(在較高溫度)與奈米粒子生長步驟(在較低溫度)分離以獲得單分散性。此等分離步驟係藉由快速將一或兩種前驅體注入熱配位溶劑(若不存在,則含有其他前驅體)獲得,其引發粒子成核。在注入時冷卻劑溶液之突然添加隨後降低反應溫度(所添加溶液之體積係約全部溶液之1/3)及抑制進一步成核,從而維持狹窄奈米粒度分佈。此方法可在可將一種溶液快速添加至另一種同時保持貫穿該反應之均勻溫度小規模合成時效果良好。然而,在較大製備規模中,藉以需要大體積溶液快速注入另一者,溫差可在該反應中發生,其可導致大粒度分佈。此外,需要進行數個尺寸選擇性純化步驟對於生產大量QD而言係不實際的。
美國專利第7,588,828號、第7,803,423號、第7,985,446號及第8,062,703號(本文共同地指「種子專利」),該等專利案全部內容以引用之方式併入本文中,描述用於製備單分散QD群體之合成方法,其不依賴上述熱注射方法及尺寸選擇性純化步驟。簡言之,該方法涉及使用在溶液中充當QD半導體材料成核模板之分子簇「種子」化合物。該簇化合物充當種子或成核點,其上可引發奈米粒子生長。以此方式,高溫成核步驟對引發奈米粒子生長係非必要的,由於適宜成核點已經藉由分子簇提供於該系統中。藉由提供與在上述方法中採用之成核點相比更加均勻之成核點,該合成提供基本上係單分散之QD群體。該分子種子方法之一顯著優點係其易於擴大規模。
不論QD奈米粒子係如何製備,關於外部無機表面原子之原子結合係不完全的。該表面填充有高反應性「懸掛鍵」,其可導致粒子聚
結。此等未配位表面原子亦可提供具表面狀態之激子,其可提供輻射發射之替代復合途徑。此等途徑係非所需及導致較低發光。此外,未配位原子對氧化更易感。
與未配位懸掛鍵相關聯之問題可部分藉由使用保護性有機基團鈍化(覆蓋)「裸」表面原子而克服。粒子之覆蓋或鈍化不僅防止粒子聚結發生,其亦保護粒子不受其周圍化學環境影響及提供電子穩定化(鈍化)至粒子。該封蓋劑通常係路易士鹼化合物或其他結合至粒子最外無機層之表面金屬原子之供電子化合物(例如,結合至核殼QD粒子之最外殼)。當QD殼合成在供電子溶劑(諸如TOP/TOPO)中進行時,該封蓋劑可簡單地係附著於QD表面之溶劑分子。在使用非供電子溶劑情況下,可將富電子封蓋劑添加至該殼合成。例如,若溶劑諸如THERMINOL用於成殼反應時,可必要地添加供電子化合物,諸如肉豆蔻酸至該反應混合物以提供封蓋配位體。
當供電子封蓋配位體提供一些穩定性及表面鈍化時,眾多此等配位體僅弱黏附於QD奈米粒子表面。該封蓋配位體之解吸附在表面上余留空位,其可導致聚結、沉澱,及其係對QD之量子效率有害。一種解決該弱結合封蓋配位體問題之方法已經使用含有官能團之封蓋配位體,該官能團對QD表面之原子具有特定結合親和力。例如,硫醇化合物之硫對眾多金屬原子(諸如鋅,其係QD殼半導體材料之常用組分,諸如ZnS及ZnSe)具有親和力。由此,硫醇已經廣泛用作QD之封蓋配位體。但是硫醇封蓋配位體亦可解吸附,在QD表面余留成問題之空位。一種硫醇配位體解吸附之可能機制係經由在QD表面相鄰硫醇間形成二硫鍵,接著解吸附該二硫化物。另一硫醇封蓋配位體之問題係,在一些情況下,空間位阻可阻止完全表面覆蓋。換言之,一旦獲得特定表面覆蓋,額外硫醇分子空間上阻止達到QD表面結合,甚至在表面仍然有大量懸掛鍵未填充。由此需要用於QD之更感性封
蓋配位體以最大化QD材料之效能及穩定性。
本文揭示之二硫配位體解決上文描述之問題。實例二硫配位體包括二硫代胺基甲酸鹽配位體。本文描述之強結合配位體係有能力配位至該奈米粒子表面上之陽性及陰性原子二者。該配位體係雙配位基及由此其對該QD表面之接近係不同於單配位基配位體接近般受空間位阻。所揭示配位體可由此完全使該QD表面飽和。
根據一實施例,將具有結合該QD表面電正性原子之基團的第一配位體添加至該QD及隨後添加具有結合該電負性原子之基團的第二配位體。例如,若該最外殼包括ZnS,則一種配位體可優先結合至Zn原子,其在該殼表面係電正性及第二配位體可優先結合至S原子,其更具電負性。藉由在該QD表面結合較大數量之可結合位點,本文揭示之二硫代胺基甲酸鹽配位體增進該等QD奈米粒子之穩定性及光學特性。
101‧‧‧添加核前驅體及分子簇
102‧‧‧監測核生長
103‧‧‧單離核
104‧‧‧使核與殼前驅體反應
105‧‧‧將配位體交換為二硫代胺基甲酸鹽配位體
圖1係一種根據本發明用於製備含二硫代胺基甲酸鹽配位體之QD的方法的流程圖。
本文描述之二硫代胺基甲酸鹽配位體可用作一般任何類型半導體QD奈米粒子之封蓋配位體。特別有用的QD奈米粒子係如在美國專利第7,588,828號、第7,803,423號、第7,985,446號及第8,062,703號(本文共同地指「種子專利」)中描述般製備,該等專利案全部內容以引用之方式併入本文中。圖1闡明此一種製備QD奈米粒子之方法。簡言之,該方法涉及在分子簇化合物存在時使核材料前驅體反應,其充當晶體生長之種子(101)。該種子專利描述多種前驅體材料及分子簇化合物。作為一實例,適宜用於InP基核之前驅體化合物必須提供銦
源及磷源。例如,該銦源可係肉豆蔻酸銦及該磷源可係參(三甲基矽基)膦。應瞭解可使用其他銦源及磷源。
該核形成反應可在分子種子化合物存在時進行。適宜分子種子化合物在上文引用之種子專利中詳盡描述。一種適宜分子種子化合物之實例係在美國專利第8,062,703號中描述之硫化鋅基分子種子化合物。該核前驅體化合物及該分子種子化合物在溶劑中,在該等種子專利及美國專利公開案第2010/0068522號中描述之條件下加熱,該等專利案全部內容以引用之方式併入本文中。一般而言,非供電子溶劑用於該反應。適當溶劑之一實例係THERMINOL®(SOLUTIA INC.,ST.LOUIS MISSOURI 63141)。
吾人期望在該核合成期間監測核生長102(例如,經由該QD核之光學性質)。例如,吸收光譜可作為該QD核生長監測及當該核達到適宜尺寸以產生期望之吸收及/或發射光譜時,該反應可停止。一旦獲得該期望光學值及該反應停止,可例如藉由過濾單離該等核103。吾人期望將非溶劑添加至該反應混合物以引發該等核沉澱。一旦該等核經單離,其可與殼前驅體反應104以在該等核上生長一或多個半導體殼。吾人期望在使該等核與該等殼前驅體反應之前例如藉由從該等核蝕刻少量該材料來預處理該等核。一種酸,諸如氫氟酸可用於蝕刻該核。
該等殼前驅體反應以在該等QD核上形成半導體材料之殼。若在該等成殼反應期間使用非配位溶劑,則需要在該成殼反應期間添加配位體諸如肉豆蔻酸以使該成殼反應穩定。若使用配位溶劑諸如TOP/TOPO,則溶劑分子本身可充當配位體以使該成殼反應穩定。在任一情況下,該等QD之最外半導體表面結合至封蓋配位體。
下一步驟係至少將一部分該封蓋配位體與所揭示之二硫配位體交換。該二硫配位體具有該一般結構(1):
二硫配位體之實例包括二硫代胺基甲酸鹽配位體。適宜第一二硫代胺基甲酸鹽封蓋配位體之實例由結構(2)及(3)表示:
其他適宜二硫配位體包括烷基二硫代碳酸鹽(即黃原酸鹽)配位體,具有一般結構(4):
該(等)R基團可係任何官能團,及一般係烴。實例包括烷基或芳基。一實例係乙基。根據一些實施例,該(等)R基團可包含具有定制該等QD親水性能力之官能團,例如使該等QD更易溶於親水環境。此R基團之一實例係在C12位置具有羧酸官能度之C12烴鏈。一旦適宜地配位至該等點表面,該羧酸可經鹼去質子化及該等點轉移至親水介質。或者,該(等)R基團可係兩親性基團諸如PEG(聚乙二醇)。
第一二硫封蓋配位體可經交換以結合至該表面上之電正性原子。例如,該二硫封蓋配位體可結合至ZnS或ZnSe表面上之鋅。該第一二硫封蓋配位體化合物(1)至(4)可作為鈉鹽或鉀鹽提供。該二硫配位體可作為粉末或含於溶劑諸如THERMINOL中提供。
適宜二硫配位體之另一實例由結構(5)表示:
在結構(5)中,R係如上文定義及R'通常係烷基。結構(5)之化合物可以單體及二聚體形式存在。當R'係乙基時,該單體形式係主要種類。根據結構(5)之化合物具有配位至表面硫化物及/或硒離子之巨大潛力,由此滿足金屬(Zn)原子之較佳配位。
二硫代胺基甲酸鋅,諸如在上文結構(5)中闡明,已經用作ZnS奈米粒子之單一源前驅體。彼等化合物係用於在InP核奈米粒子上沉積ZnS殼之單一源前驅體之可行候選。然而,二硫代胺基甲酸鋅需要高溫以使其分解。此等高溫不利地影響InP核奈米粒子之效能。若該二硫代胺基甲酸鋅在胺存在時提供,則分解溫度顯著降低。然而,將胺添加至InP奈米粒子對輻射效率具有特別激烈之淬滅效應。
本申請人已經發現若將二硫代胺基甲酸鋅「預配位」至胺,則二硫代鋅化合物,諸如結構(2)、(3)、及(4)、與結構(5)之鋅錯合物可用作單一源成殼前驅體(即,在核奈米晶體上提供ZnS殼元素之單一源前驅體)。另一適宜成殼前驅體係胺配位之烷基硫代磷酸鋅,即,具有以下結構(6)之二硫配位體的胺配位化合物:
(R=烷基)
胺與二硫代胺基甲酸鋅之預配位允許在成殼期間以胺與二硫代胺基甲酸鋅之1:1比例將該胺及該二硫代胺基甲酸鋅引入奈米粒子核溶
液。由此,無游離胺可參與核表面之淬滅反應。二硫代胺基甲酸鋅之分解溫度適宜地由胺降低,但當游離胺存在時未觀察到不利的淬火效應。適宜胺實例包括具有長烴部分之胺。特別適宜之胺係油醯胺。
游離胺之淬火效應由在油醯胺存在及不存在時使InP合金基核成殼來論證。InPZnS合金基核基本上如在美國專利第7,558,828號中描述般製備。將兩個InP合金基核樣品各懸浮於THERMINOL中。將乙酸鋅(0.862g)添加至各混合物及將該等混合物加熱至230℃持續2小時。將十二硫醇(1.69mL)添加至兩混合物及將油醯胺(0.2mL)添加至該等混合物中之一者。兩混合物允許再反應1½小時。
在缺乏油醯胺時成殼之量子點顯示在644nm具有94nm之半峰全寬(FWHM)之光致發光及75%之量子產率(QY)。在油醯胺存在時成殼之量子點顯示在644nm具有90nm之FWHM之光致發光及62%之量子產率(QY)。在胺存在時成殼樣品之較低QY闡明該胺之淬火效應。
InPZnS合金基核係如在美國專利第7,588,828號中一般描述來製備。將該等核懸浮在THERMINOL(40mL)中,將乙酸鋅(5.76g)、肉豆蔻酸(1.5g)、硬脂酸鋅(11.32g)添加至其中。在180℃加熱該混合物及隨後添加二乙基二硫代胺基甲酸鋅(2.295g)及留置20分鐘。觀察到高濁度及該反應混合物之光致發光仍然很低,此表明在該溫度下之低反應性/溶解性。將該混合物加熱至230℃及留置3小時及該粉末逐漸地溶解但QY自始至終仍然很低。
InPZnS合金基核係在實例2描述之相同條件下成殼,除在180℃下將油醯胺(5mL)添加至該混合物隨後添加二乙基二硫代胺基甲酸鹽
之外。將該混合物在180℃下再加熱20分鐘,產生在523nm具有53nm之FWHM之光致發光峰及73%之QY之量子點。實例2與3間之不同表明胺對成殼係重要的。
如美國專利第7,588,828號中一般描述所製備之InPZnS合金基核係如實例3描述般成殼,除在添加至成殼反應之前,該乙基二硫代胺基甲酸鋅首先與油醯胺藉由在氮氣下使用設置在50℃之水浴將兩者預混合在一起來錯合。該成殼反應產生具有75%之發光QY之量子點。相似反應產生具有高達85%之發光QY之量子點。
如美國專利第7,588,828號中一般描述所製備之InPZnS合金基核係如在實例4描述般成殼,除使用黃原酸鋅代替二乙基二硫代胺基甲酸鋅之外。在100℃下,於真空中攪拌含於THERMINOL中之InPZnS合金基核(500mg)、肉豆蔻酸(1.5g)、乙酸鋅(2.4g),及硬脂酸鋅(5.3g)1小時及隨後加熱至215℃,再冷卻至140℃。將含於THERMINOL(5mL)中之乙基黃原酸鋅(0.97g)與油醯胺(1.05mL)之預混合溶液添加至該核溶液。攪拌該溶液1小時,隨後在180℃下攪拌1小時。添加辛醇(2.4mL)及再攪拌該溶液30分鐘。該反應產生具有85%之發光QY之量子點。
雖然已經顯示及描述本發明之特定實施例,但是其等並非意在限制本專利覆蓋之範圍。熟習此項技術者應瞭解,可在不脫離由隨後申請專利範圍照字面及等效覆蓋之本發明範圍下進行各種變化及改良。
101‧‧‧添加核前驅體及分子簇
102‧‧‧監測核生長
103‧‧‧單離核
104‧‧‧核與殼前驅體反應
105‧‧‧將配位體交換為二硫代胺基甲酸鹽配位體
Claims (4)
- 一種量子點(QD)奈米粒子,其包括複數個第一二硫代碳酸鹽封蓋配位體。
- 如請求項1之QD奈米粒子,其中該二硫代碳酸鹽封蓋配位體具有以下一般結構:
- 如請求項2之QD奈米粒子,其中R及R'係烴。
- 如請求項2之QD奈米粒子,其中該R基團係在C12位置具有羧酸官能度之C12烴鏈。
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