CN116177550B - Surface passivation method and application of silicon nano material - Google Patents
Surface passivation method and application of silicon nano material Download PDFInfo
- Publication number
- CN116177550B CN116177550B CN202310222488.1A CN202310222488A CN116177550B CN 116177550 B CN116177550 B CN 116177550B CN 202310222488 A CN202310222488 A CN 202310222488A CN 116177550 B CN116177550 B CN 116177550B
- Authority
- CN
- China
- Prior art keywords
- silicon
- nanomaterial
- nano material
- silicon nano
- silicon nanomaterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 146
- 239000010703 silicon Substances 0.000 title claims abstract description 146
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 130
- 238000000034 method Methods 0.000 title claims abstract description 82
- 238000002161 passivation Methods 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 54
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000002444 silanisation Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000005495 cold plasma Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- BLIQUJLAJXRXSG-UHFFFAOYSA-N 1-benzyl-3-(trifluoromethyl)pyrrolidin-1-ium-3-carboxylate Chemical compound C1C(C(=O)O)(C(F)(F)F)CCN1CC1=CC=CC=C1 BLIQUJLAJXRXSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 description 26
- 230000008569 process Effects 0.000 description 21
- 239000010410 layer Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 238000006459 hydrosilylation reaction Methods 0.000 description 17
- 238000004020 luminiscence type Methods 0.000 description 13
- 230000007547 defect Effects 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 11
- 230000006798 recombination Effects 0.000 description 11
- 238000005215 recombination Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000007847 structural defect Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WZEYZMKZKQPXSX-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1.CC1=CC(C)=CC(C)=C1 WZEYZMKZKQPXSX-UHFFFAOYSA-N 0.000 description 1
- 241001274197 Scatophagus argus Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- CIYWARODCYRXIC-UHFFFAOYSA-N dec-1-ene Chemical compound CCCCCCCCC=C.CCCCCCCCC=C CIYWARODCYRXIC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a surface passivation method and application of a silicon nanomaterial, which belong to the technical field of nanomaterials, and specifically comprise the following steps: (1) Applying an active oxidation procedure to the unsupported silicon nanomaterial to form a dense oxide layer on the surface of the unsupported silicon nanomaterial; etching the surface oxide layer completely by using high-concentration hydrofluoric acid to obtain a hydrogen-terminated silicon nanomaterial; (2) Under the condition of isolating water and oxygen, performing silanization reaction by utilizing olefin and the hydrogen-terminated silicon nanomaterial, and further cleaning and purifying the obtained crude product to obtain the silicon nanomaterial with the surface carbon chain terminated. Compared with the traditional method, the method of the invention increases the prepositive active oxidation procedure, builds a compact oxide thin layer on the surface of the silicon nano material, can prepare the silicon nano material with higher carbon chain coverage rate and lower surface dangling bond number, and can reach 60 percent of fluorescence quantum yield.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a surface passivation method and application of a silicon nano material.
Background
Along with the coming limit of moore's law, microelectronic technology reaches a bottleneck, and optical interconnection in optoelectronic technology has advantages of no interference from external fields, high transmission speed, low energy consumption, high density and the like relative to electrical interconnection, and is considered as one of the directions of the next-generation chip technology development. However, silicon-based light sources are a difficult problem to be broken through in the optical interconnection technology at present, and particularly, no perfect solution exists for a light source material in the near infrared light emitting range. Silicon nanomaterials are one of the potentially important directions. Silicon materials are widely used in the modern integrated circuit industry, photovoltaic and optoelectronic device fields, and have a solid application foundation. Although the silicon material is an indirect band gap semiconductor material, phonons are required to participate in the optical transition process to cause low carrier radiation recombination efficiency and difficult to be practically applied in the field of luminescence, the silicon material can be quantized to obtain the silicon nanomaterial forming a collimation band gap, the silicon nanomaterial benefits from quantum confinement effect, the silicon nanomaterial has the characteristic of tunable luminescence wavelength after size quantization, and meanwhile, the silicon nanomaterial also has good biological and environmental compatibility, and becomes an important near infrared fluorescent material.
Optimization of the optical properties of silicon nanomaterials relies on both dimensional and surface control. First, the size of the silicon nanoparticles determines the extent of the quantum confinement effect, and it is believed that the silicon nanomaterial will exhibit a quasi-direct band gap when its size is smaller than Yu Jizi Bohr radius (5 nm), and is capable of radiative fluorescence (Priolo, F.et al silicon nanostructures for photonics and photovoltaics. Nature nanotech. (2014), 9, 19-32). Studies have further quantitatively indicated the relationship of fluorescence peak position, fluorescence lifetime and size of silicon nanomaterials, with the smaller the silicon nanoparticle size, the more and less the probability of non-radiative recombination of excitons, and the more and less the probability of radiative recombination (Liu, x.et al. Optimum Quantum Yield of the Light Emission from 2to 10nm Hydrosilylated Silicon Quantum Dots.Part.Part.Syst.Charact. (2016), 33:44-52), since the surface effect increases as the silicon nanomaterial size decreases. Therefore, at a certain size, the optical properties of the silicon nanomaterial are mainly controlled by the surface structure.
The type, density and surface ligand structure of the surface defects affect the optical properties of the silicon nanomaterial together, and great effort is required to avoid defects and dangling bonds which cause non-radiative recombination of excitons, and the silicon nanomaterial is usually subjected to surface passivation to obtain stable and efficient luminescence. The most widely applied passivation silicon nano material is a hydrosilylation method, alkene or alkyne is used as a modifier to passivate the hydrogen-terminated silicon nano material under certain reaction conditions, and finally the carbon chain-terminated silicon nano particles with the surfaces connected through covalent bonds are obtained. Around the hydrosilylation method, various improvements have been proposed in the prior art, such as: the hydrosilylation process was modified using high temperature hydrosilylation (Jonathan G.C. solvent. Synthesis, surface functionalization, and properties of freestanding silicon nanocrystallines.chemical Communications (2006), 40:4160-8), using ultraviolet light assisted hydrosilylation (F.Hua et al. Effect Surface Grafting of Luminescent Silicon Quantum Dots by Photoinitiated hydrosilation.Langmuir (2005), 21,13,6054-6062), using in situ gas phase processes (S.L. Weeks et al gas-Phase Hydrosilylation of Plasma-Synthesized Silicon Nanocrystals with Short-and Long-Chain Alkynes [ J ]. Langmuir (2012), 28 (50): 17295-301), using catalysts to accelerate room temperature hydrosilylation (M.H. Mobarok et al Angew.chem. Int. Effect. (2017), 56,6073) or using free radical initiators (O.Taisei et al. Dening Efficient Si Quantum Dots and LEDs by Quantifying Ligand effect ACS.2028), material (14,1,1373-8).
However, in the existing researches, these surface passivation methods have not proposed means capable of effectively solving the steric hindrance effect between the silicon nanoparticles, and it is difficult to obtain high surface carbon chain coverage, and the number of surface defects of the silicon nanomaterial cannot be effectively limited, so that the optical property optimization effect on the silicon nanomaterial is limited, and especially for the silicon nanomaterial in the near infrared light emitting band, the fluorescence quantum yield needs to be improved. More importantly, an active and quantifiable surface structure design method is not available at present to further optimize the light emitting effect of the silicon nanomaterial.
In view of the foregoing, there is a need for a simple and efficient passivation method for silicon nanomaterials to obtain near infrared luminescent silicon nanomaterials with high fluorescence quantum yields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a surface passivation method of a silicon nano material, which has simple procedure and easy quantitative production, and can effectively solve the problems of low surface carbon chain coverage rate and more non-radiative recombination centers of the silicon nano material, thereby remarkably improving the optical performance of the obtained silicon nano material.
The technical scheme adopted is as follows:
a surface passivation method of a silicon nano material comprises the following steps:
(1) Applying an active oxidation procedure to the unsupported silicon nanomaterial to form a dense oxide layer on the surface of the unsupported silicon nanomaterial; further completely etching the surface oxide layer by using high-concentration hydrofluoric acid to obtain a hydrogen-terminated silicon nanomaterial;
(2) Under the condition of isolating water and oxygen, performing silanization reaction on the olefin and the hydrogen-terminated silicon nanomaterial, and further cleaning and purifying the obtained crude product to obtain the silicon nanomaterial with the surface carbon chain terminated.
Because the surface structure of the silicon nano material shows remarkable regulation and control effects on the optical properties of the silicon nano material, great effort is required to avoid defects and dangling bonds which can cause non-radiative recombination of excitons, the hydrosilylation method proposed in the prior study is to directly treat the silicon nano particles by using hydrofluoric acid, the quantity of exposed silicon hydrogen bonds is limited, and meanwhile, structural defects cannot be effectively treated, so that the surface defects are often limited by the practically obtained surface carbon chain coverage rate and cannot be passivated ideally.
Compared with the traditional silicon nanomaterial passivation method, the silicon nanomaterial surface passivation method has the advantages that a prepositive active oxidation procedure is added in a single direct hydrosilylation process, the active oxidation procedure is beneficial to constructing a compact oxide thin layer on the surface of unsupported silicon nanomaterial such as silicon nanoparticles, and adverse effects (surface structure defects and adverse effects of surface dangling bonds on the luminescent property of the silicon nanomaterial) of the surface effect introduced after the silicon nanomaterial is nanocrystallized can be effectively avoided by combining with a subsequent complete etching process, so that non-radiative recombination sites are reduced. It should be noted that etching away a sufficiently dense thin oxide layer helps to passivate structural defects near the surface layer, while introducing a greater number of more densely distributed silicon-hydrogen bonds (Si-H) to the surface of the silicon nanomaterial x X=1, 2, 3), and free radicals that play a critical role in the silylation process, thereby enabling more organic carbon chains to be attached to the silicon surface for capping, the density of surface dangling bonds being reduced by an order of magnitude (surface dangling bond density less than or equal to 10) 12 cm -2 ) The optimal fluorescence quantum yield of the silicon nano material is 60% (the luminescence peak position is 762 nm) and 55% (the luminescence peak position is 855 nm), and the problems that the silicon nano material in the prior art has poor luminescence effect in the near infrared band and is difficult to be practically applied are overcome.
In the invention, the unsupported silicon nanomaterial can be crystalline or amorphous; preferably, the unsupported silicon nanomaterial is crystalline silicon nanoparticles prepared by a cold plasma method, the particle size range is 2-10nm, and the specific preparation method is as follows: siH is added to 4 And introducing rare gas mixture into a cold plasma reaction chamber, and generating silicon nano particles under the conditions that the gas pressure is 3mbar and the plasma power and the radio frequency power are 40-70W.
The active oxidation procedure comprises natural oxidation in a constant temperature and humidity drying oven or heat treatment oxidation in air atmosphere; preferably, the thickness of the compact oxide layer is more than 1.0nm.
The compactness and thickness of the oxide layer are controlled by the time of natural oxidation and the temperature and duration of heat treatment oxidation; preferably, the conditions of constant temperature and humidity are respectively 15-40 ℃,20-40%, and the natural oxidation time is more than or equal to 7 days; preferably, the heat treatment oxidation condition is that the temperature is 200-500 ℃ and the duration is 1-3 hours.
Further preferably, in the natural oxidation process, the constant temperature and humidity conditions are respectively 15-40 ℃ and 20-40%, and the natural oxidation time period is more than 7 days.
Still more preferably, the conditions of constant temperature and humidity during the natural oxidation are 25℃and 37%, respectively, for 150 days.
Further preferably, the heat treatment temperature of the heat treatment oxidation is 350-400 ℃ and the heat treatment time period is 1-3 hours.
Still more preferably, the heat treatment temperature of the heat treatment oxidation is 400℃and the heat treatment time period is 2 hours.
Preferably, the high-concentration hydrofluoric acid is hydrofluoric acid with the volume fraction of more than or equal to 40%. The high-concentration hydrofluoric acid can completely etch oxide on the surface of the silicon nano material to obtain the silicon nano material with the surface hydrogen end capped, expose as many silicon hydrogen bonds and free radicals as possible, and passivate structural defects close to the surface layer to a great extent.
Specifically, the etching steps are as follows: dispersing the silicon nano material with the oxide layer on the surface in ethanol to obtain a dispersion liquid, adding hydrofluoric acid with the volume fraction of more than or equal to 40% into the dispersion liquid, fully stirring for 1-3 minutes at room temperature, centrifuging, and cleaning to completely remove the hydrofluoric acid and the ethanol to obtain the hydrogen-terminated silicon nano material.
Preferably, the olefin is an olefin having a carbon chain length of from C7 to C12.
Specifically, the silylation step is: the olefin, the hydrogen end capped silicon nano material and xenon difluoride are reacted in an organic solvent for 4 to 6 hours at the temperature of 100 to 180 ℃ to remove the organic solvent, and the silanization of the silicon nano material is completed, so that a crude product is obtained.
Further preferred, the olefin is 1-decene.
It is further preferred that the organic solvent is removed by rotary evaporation at a temperature of 100-140 ℃.
Further preferably, the organic solvent is mesitylene.
Specifically, the steps of cleaning and purifying are as follows: dispersing the crude product into toluene, adding methanol, and re-precipitating the silicon nano material with the end capped by the surface carbon chain.
Preferably, in the cleaning and purifying process, the volume ratio of the methanol to the toluene is more than or equal to 1:1, and the mixed solution is obviously turbid after the methanol is added.
The surface passivation method of the silicon nano material comprises the steps of applying an active oxidation procedure to the free-standing silicon nano material prepared by a cold plasma method, completely etching oxide on the surface of the silicon nano material by using high-concentration hydrofluoric acid after a compact surface oxide layer is obtained, obtaining the silicon nano material with a hydrogen end-capped surface, exposing as many silicon hydrogen bonds and free radicals as possible, passivating structural defects close to the surface layer to the greatest extent, performing silanization treatment on the silicon nano material with the hydrogen end-capped surface, connecting olefin with specific carbon chain length to the surface of the silicon nano material through covalent bonds, and cleaning and purifying to realize the passivation of an organic carbon chain of the final silicon nano material.
The invention also provides a silicon nanomaterial, which is prepared by the method.
Preferably, the particle size of the silicon nano material is 3-5nm, the surface coverage rate is more than or equal to 60%, and the surface dangling bond density is less than or equal to 10 11 cm -2 The fluorescence lifetime is more than or equal to 110 mu s, and the fluorescence quantum yield is more than or equal to 50%.
The invention also provides a silicon-based light-emitting device, which comprises the silicon nanomaterial;
preferably, the silicon nanomaterial may be used as a light emitting active layer of a silicon-based light emitting diode device.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides the surface passivation method of the silicon nano material, which can obtain higher carbon chain coverage rate, lower surface dangling bond number and high fluorescence quantum yield, and the surface structure of the silicon nano material is controlled to obviously reduce the adverse effect of surface defects, improve the optical performance of the silicon nano material, and the optimal fluorescence quantum yield can reach 60% in the near infrared band range.
(2) In the prior art, the surface carbon chain coverage rate of the passivated silicon nano material is at a low level and cannot be effectively controlled, but in the invention, the strategy of firstly oxidizing and then passivating the surface of the silicon nano material can control the quantity and distribution of silicon hydrogen bonds after the hydrogenation process by controlling the thickness and the compactness of a surface oxide layer, further control the carbon chain coverage rate of the surface of the silicon nano material after silanization, control the quantity of surface dangling bonds, and overcome the problem of low coverage rate of carbon chain ligands on the surface of the silicon nano material in the traditional passivation method.
(3) The method is suitable for surface passivation of unsupported silicon nano materials prepared by various ways, the effect of active oxidation is independent of control on a single sample, the surface passivation can be completed through natural oxidation or heat treatment oxidation, and the surface passivation method is a prepositive improved procedure, does not obviously change the existing hydrosilylation operation flow, and is beneficial to cost control and mass production and application.
Drawings
FIG. 1 is a schematic diagram of the synthesis of silicon nanoparticles prepared by cold plasma process;
FIG. 2 is a schematic diagram of a silicon nanoparticle surface forming a dense oxide layer by an active oxidation process;
FIG. 3 is a schematic illustration of a hydrosilylation reaction process;
FIG. 4 is a fluorescence emission (PL) spectrum of the silicon nanomaterial produced in example 1;
FIG. 5 is a fluorescence excitation (PLE) spectrum of the silicon nanomaterial produced in example 1;
FIG. 6 is an ultraviolet absorption spectrum of the silicon nanomaterial prepared in example 1;
FIG. 7 is a Fourier transform Infrared Spectroscopy (FTIR) test results of silicon nanomaterials obtained from different oxidation treatments;
FIG. 8 shows Electron Paramagnetic Resonance (EPR) test results of silicon nanomaterials obtained by different oxidation treatments;
FIG. 9 is a graph showing the results of a life test fit of silicon nanomaterials obtained from different oxidation treatments;
FIG. 10 is the effect of natural oxidation time on fluorescence quantum yield (PLQY) of surface carbon chain capped silicon nanoparticles.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Specifically, the silicon nanomaterial produced in examples and comparative examples was subjected to performance detection by the following method;
testing photoluminescence spectrum of the silicon nano material by adopting a fluorescence spectrometer;
an ultraviolet-visible absorption spectrometer is adopted to test the absorption spectrum of the silicon nano material;
testing the surface functional group structure of the silicon nano material by using a Fourier transform infrared spectrometer;
using an electron paramagnetic resonance spectrometer to test the surface dangling bond density of the silicon nano material;
the detection method of the luminescence life of the silicon nanomaterial comprises the following steps: detecting a luminescence attenuation curve of the silicon nanomaterial by using a fluorescence spectrometer, wherein the excitation wavelength is 467nm and the frequency is 100Hz, fitting the luminescence attenuation curve by using the following formula (1), and finally calculating the luminescence life by using the following formula (2).
Wherein I (t) is the value of the intensity of the luminescence decay curve with time t, A 1 And A 2 Is the fitting coefficient τ 1 And τ 2 Respectively fitting to obtain a fast life and a slow life, wherein tau is the luminescence life;
the detection method of the fluorescence quantum yield of the silicon nano material comprises the following steps: the fluorescence quantum yield of the silicon nano material is measured by a fluorescence spectrometer, the fluorescence quantum efficiency refers to the ratio of the photon number of secondary radiation fluorescence emitted by the material to the photon number of primary radiation of absorption excitation light in unit time in the photoluminescence process, and the fluorescence quantum efficiency is an important parameter for representing the fluorescence performance of the material, and an integrating sphere accessory is required to be equipped in the test process. The fluorescence quantum yield (PLQY) was calculated using the following formula (3).
Wherein P is sample em Is the integrated intensity of the emission spectrum of the test sample,is the integrated intensity of the emission spectrum of the reference sample, < >>Is the integrated intensity of the scattered signal of the reference sample, L sample scat Is the integrated intensity of the scattered signal of the test sample.
Example 1
(1) SiH is added to 4 Introducing rare gas mixture into cold plasma reaction chamber, inUnder the conditions of air pressure of 3mbar and plasma power of 40-70W, crystalline silicon nano particles with the particle size of 4nm are prepared (the synthetic schematic diagram of the silicon nano particles prepared by a cold plasma method is shown as figure 1), then an active oxidation procedure is applied to the silicon nano particles, the silicon nano particles are stored in a constant temperature and humidity cabinet with the temperature of 25 ℃ and the humidity of 37 percent and naturally oxidized for 150 days, and a compact oxide layer with the thickness of about 1.4nm is formed on the surfaces of the particles, and the schematic diagram is shown as figure 2;
(2) Weighing 50mg of silicon nano-particles with a compact oxide layer, ultrasonically dispersing the silicon nano-particles in 10mL of ethanol, adding 2.5mL of hydrofluoric acid with the volume fraction of 40%, fully stirring for 1 min at room temperature to completely etch oxide on the silicon surface, centrifuging, pouring out clear liquid, and then dispersing in 10mL of mesitylene to obtain hydrogen-terminated silicon nano-particles;
(3) A three-neck flask, a condenser tube and a rubber catheter are used for constructing a reaction passage, argon is introduced in advance for cleaning for 30 minutes to obtain a reaction environment isolated from water and oxygen, 15mL of mesitylene (mesitylene) and 5mL of 1-decene (1-decene) are sequentially added into the reaction passage, and after stirring and deoxidizing for 30 minutes, hydrogen-terminated silicon nano particles and xenon difluoride (XeF) are sequentially added into the reaction system 2 ) Reacting for 6 hours at 160 ℃ to prepare surface carbon chain end capped silicon nano particles (a specific hydrosilylation reaction process schematic diagram is shown in figure 3) dispersed in the mesitylene, evaporating organic solvent in the solution by using a rotary evaporator at 100 ℃, and separating out a crude product of the surface carbon chain end capped silicon nano particles;
and dispersing, dissolving and transferring the crude product into a centrifuge tube by using 2mL of toluene, adding 2mL of methanol into the centrifuge tube until the solution becomes turbid, re-separating out silicon nano particles with uniform size and low organic solvent content and end-capped by surface carbon chains, and after centrifugation, re-dispersing the solid particles into toluene and preserving for later use.
Results and analysis: the optical properties of the silicon nano material obtained in the embodiment 1 are shown in fig. 4-6, and the optimal excitation wavelength of the silicon nano particles is 467nm (fig. 5) and the central peak position of the fluorescence spectrum is 762nm (fig. 4) through detection of a fluorescence spectrometer; the absorption spectrum (FIG. 6) shows that with the excitation light sourceThe energy absorbed by the silicon quantum dots is correspondingly increased by the energy improvement; the structure of the surface functional group is shown in figure 7, and the coverage rate of the surface carbon chain is 67.3 percent; in addition, the surface dangling bonds of the silicon nano material are shown in fig. 8, and the density of the surface dangling bonds is calculated to be 1.55 x 10 10 cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The life test and fitting results are shown in FIG. 9, and the calculated luminescence life is 114.2 mu s; as shown in fig. 10, the fluorescence quantum yield of the silicon nanomaterial was 60.3%.
Example 2
The surface passivation method of the silicon nanomaterial in this embodiment is different from that of embodiment 1 only in that the number of days of natural oxidation is 7 days in the active oxidation process.
Results and analysis: the test result of the surface functional group structure of the silicon nanoparticle obtained by the example 2 is shown in fig. 7, the EPR test result is shown in fig. 8, and the surface carbon chain coverage rate is calculated to be 51.0%, and the dangling bond density is calculated to be 4.5×10 10 cm -2 This is detrimental to passivation of non-radiative recombination centers on the surface of the silicon nanomaterial, resulting in a fluorescence lifetime of 81.7 μs for the silicon nanoparticles (test results as shown in fig. 9), a fluorescence quantum yield of 22.98%, which is significantly lower than that of comparative example 1. The longer the natural oxidation time is, the more compact the silicon surface oxide layer can be obtained, and the more favorable the silicon nano material with good passivation effect can be obtained in the subsequent hydrosilylation process.
Example 3
The surface passivation method of the silicon nanomaterial in this embodiment is different from that of embodiment 1 only in that the active oxidation procedure is a heat treatment at 350 ℃ in an air atmosphere for 2 hours.
Results and analysis: the test result of the surface functional group structure of the silicon nanoparticle obtained by the example 3 is shown in fig. 7, the EPR test result is shown in fig. 8, and the surface carbon chain coverage rate is 49.8% and the dangling bond density is 3.8×10 10 cm -2 This is detrimental to passivation of non-radiative recombination centers on the surface of the silicon nanomaterial, resulting in a fluorescence lifetime of the silicon nanoparticle of 92.5 μs (test results as in FIG. 9), a fluorescence quantum yield of 19.6%, higher than that of comparative example 1, but significantly lower than that of real worldExample 1. This shows that the use of the heat treatment oxidation procedure can exert an optimized effect similar to that of the natural oxidation procedure, but the short-time heat treatment results in insufficient densification of the thin oxide layer on the silicon surface, while the introduction of thermal stress to generate defects is unavoidable, resulting in inferior luminescent properties of the silicon nanomaterial as in example 1.
Example 4
The surface passivation method of the silicon nanomaterial in this embodiment is different from that of embodiment 1 only in that the number of days of natural oxidation is 14 days in the active oxidation process.
Results and analysis: the fluorescence lifetime of the silicon nanoparticles obtained in example 4 was 97.4 μs, the fluorescence quantum yield was 31.7%, which is significantly lower than that of comparative example 1, compared with example 1, indicating that the longer the natural oxidation time, the denser the silicon surface oxide layer can be obtained, and further the better the passivation effect of the silicon nanomaterial can be obtained in the subsequent hydrosilylation process.
Example 5
The surface passivation method of the silicon nanomaterial in this embodiment is different from that of embodiment 1 only in that the number of days of natural oxidation is 30 days in the active oxidation process.
Results and analysis: the fluorescent lifetime of the silicon nano-particles obtained in example 4 is 103.2 μs, the fluorescence quantum yield is 36.5%, and the fluorescent quantum yield is obviously lower than that of comparative example 1, compared with example 1, which shows that the longer the natural oxidation time is, the more compact the silicon surface oxide layer can be obtained, and further the silicon nano-material with good passivation effect can be obtained in the subsequent hydrosilylation process.
Example 6
The surface passivation method of the silicon nanomaterial in this embodiment is different from that in embodiment 1 only in that the active oxidation procedure is a heat treatment at 400 ℃ in an air atmosphere for 2 hours.
Results and analysis: the surface carbon chain coverage of the silicon nanoparticle obtained by example 6 was 54.0% and the dangling bond density was 3.3×10 10 cm -2 This is detrimental to passivation of non-radiative recombination centers on the surface of the silicon nanomaterial, resulting in a fluorescence lifetime of 94.7 μs for the silicon nanoparticles, fluorescence quantum yield27.0% higher than comparative example 1 and significantly lower than example 1. This shows that the use of the heat treatment oxidation procedure can exert an optimized effect similar to that of the natural oxidation procedure, but the short-time heat treatment results in insufficient densification of the thin oxide layer on the silicon surface, while the introduction of thermal stress to generate defects is unavoidable, resulting in inferior luminescent properties of the silicon nanomaterial as in example 1.
Example 7
The surface passivation method of the silicon nanomaterial in this embodiment is different from that in embodiment 1 only in that the active oxidation procedure is a heat treatment at 500 ℃ in an air atmosphere for 2 hours.
Results and analysis: the fluorescent quantum yield of the silicon nanoparticle obtained by example 7 was 16.81%, the fluorescence lifetime was 79.6 μs, higher than that of comparative example 1, and significantly lower than that of example 1. This shows that the use of the heat treatment oxidation procedure can exert an optimizing effect similar to that of the natural oxidation procedure, but the thin layer of the silicon surface oxide obtained by the short-time heat treatment is not compact enough, and the optimizing effect is inferior to that of the natural oxidation. It can also be seen that the effect of thermal stress defects introduced during the heat treatment on the luminescent properties of the silicon nanoparticles starts to dominate when the heat treatment temperature is increased to 500 ℃, resulting in a fluorescence quantum yield inferior to that of examples 2, 6.
Comparative example 1
The surface passivation method of the silicon nanomaterial in this comparative example is different from that in example 1 only in that the active oxidation process is not performed.
Results and analysis: the test result of the surface functional group structure of the silicon nanoparticle obtained by the example 2 is shown in fig. 7, the EPR test result is shown in fig. 8, and the surface carbon chain coverage rate is only 12.2% and the dangling bond density is 2.2×10 11 cm -2 . This is detrimental to passivation of non-radiative recombination centers on the surface of the silicon nanomaterial, resulting in a fluorescence lifetime of the silicon nanoparticles of only 74.21 μs and a fluorescence quantum yield of only 4.72%, which is an order of magnitude different from that obtained in example 1, indicating that the surface passivation strategy proposed in the present invention, which applies an active oxidation procedure prior to hydrosilylation, is remarkable and helps to solve the problem of the prior art of luminescent effects of silicon nanoparticles in the near infrared bandPoor and difficult to be practically applied.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. The surface passivation method of the silicon nano material is characterized by comprising the following steps of:
(1) Applying an active oxidation procedure to the unsupported silicon nanomaterial to form a dense oxide layer on the surface of the unsupported silicon nanomaterial; further completely etching the surface oxide layer by using high-concentration hydrofluoric acid to obtain a hydrogen-terminated silicon nanomaterial;
(2) Under the condition of isolating water and oxygen, performing silanization reaction on the olefin and the hydrogen-terminated silicon nanomaterial, and further cleaning and purifying the obtained crude product to obtain the silicon nanomaterial with the surface carbon chain terminated;
the unsupported silicon nano material is crystalline silicon nano particles prepared by a cold plasma method, and the particle size is 2-10nm;
the active oxidation procedure comprises natural oxidation in a constant temperature and humidity drying oven or heat treatment oxidation in air atmosphere; the thickness of the compact oxide layer is more than 1.0nm;
the constant temperature and humidity conditions are respectively 15-40 ℃ and 20-40%, and the natural oxidation time is more than or equal to 7 days; the conditions of the heat treatment and oxidation are 200-500 ℃ for 1-3 hours;
the high-concentration hydrofluoric acid is hydrofluoric acid with the volume fraction of more than or equal to 40%;
the silanization comprises the following steps: the olefin, the hydrogen end capped silicon nano material and xenon difluoride are reacted in an organic solvent for 4 to 6 hours at the temperature of 100 to 180 ℃ to remove the organic solvent, and the silanization of the silicon nano material is completed, so that a crude product is obtained.
2. The method for passivating the surface of a silicon nanomaterial of claim 1, wherein the olefin is an olefin having a carbon chain length of C7-C12.
3. The method for passivating the surface of a silicon nanomaterial according to claim 1, wherein the cleaning and purifying step specifically comprises: dispersing the crude product into toluene, adding methanol, and re-precipitating the silicon nano material with the end capped by the surface carbon chain.
4. A silicon nanomaterial characterized by being prepared by a surface passivation method of the silicon nanomaterial according to any one of claims 1 to 3.
5. A silicon-based light emitting device comprising the silicon nanomaterial of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310222488.1A CN116177550B (en) | 2023-03-09 | 2023-03-09 | Surface passivation method and application of silicon nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310222488.1A CN116177550B (en) | 2023-03-09 | 2023-03-09 | Surface passivation method and application of silicon nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116177550A CN116177550A (en) | 2023-05-30 |
| CN116177550B true CN116177550B (en) | 2024-02-27 |
Family
ID=86448697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310222488.1A Active CN116177550B (en) | 2023-03-09 | 2023-03-09 | Surface passivation method and application of silicon nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116177550B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083413A (en) * | 1995-10-19 | 2000-07-04 | Massachusetts Institute Of Technology | Metals removal process |
| JP2002527253A (en) * | 1998-10-15 | 2002-08-27 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Silicon processing method using etching process |
| CN1873923A (en) * | 2006-06-09 | 2006-12-06 | 南京大学 | Method for constructing even distributed Nano points of siliocn, Nano lines of siliocn under normal temperature |
| CN102738291A (en) * | 2012-07-07 | 2012-10-17 | 蚌埠玻璃工业设计研究院 | Silicon-based heterojunction double-side solar cell and preparation method thereof |
| WO2013168252A1 (en) * | 2012-05-09 | 2013-11-14 | 三菱電機株式会社 | Photovoltaic device and method for producing same |
| JP2014193792A (en) * | 2013-03-29 | 2014-10-09 | Bridgestone Corp | Method for producing silicon fine particles |
| JP2015140295A (en) * | 2014-01-30 | 2015-08-03 | 株式会社ブリヂストン | Method of producing silicon fine particles |
| CN109004038A (en) * | 2018-07-26 | 2018-12-14 | 东莞南玻光伏科技有限公司 | Solar battery and preparation method thereof and photovoltaic module |
| CN114664648A (en) * | 2022-03-15 | 2022-06-24 | 浙江大学 | Silicon etching method |
| CN114792744A (en) * | 2022-05-07 | 2022-07-26 | 通威太阳能(眉山)有限公司 | Solar cell and preparation method and application thereof |
| CN218160392U (en) * | 2022-09-26 | 2022-12-27 | 滁州捷泰新能源科技有限公司 | Solar cell |
-
2023
- 2023-03-09 CN CN202310222488.1A patent/CN116177550B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083413A (en) * | 1995-10-19 | 2000-07-04 | Massachusetts Institute Of Technology | Metals removal process |
| JP2002527253A (en) * | 1998-10-15 | 2002-08-27 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング | Silicon processing method using etching process |
| CN1873923A (en) * | 2006-06-09 | 2006-12-06 | 南京大学 | Method for constructing even distributed Nano points of siliocn, Nano lines of siliocn under normal temperature |
| WO2013168252A1 (en) * | 2012-05-09 | 2013-11-14 | 三菱電機株式会社 | Photovoltaic device and method for producing same |
| CN102738291A (en) * | 2012-07-07 | 2012-10-17 | 蚌埠玻璃工业设计研究院 | Silicon-based heterojunction double-side solar cell and preparation method thereof |
| JP2014193792A (en) * | 2013-03-29 | 2014-10-09 | Bridgestone Corp | Method for producing silicon fine particles |
| JP2015140295A (en) * | 2014-01-30 | 2015-08-03 | 株式会社ブリヂストン | Method of producing silicon fine particles |
| CN109004038A (en) * | 2018-07-26 | 2018-12-14 | 东莞南玻光伏科技有限公司 | Solar battery and preparation method thereof and photovoltaic module |
| CN114664648A (en) * | 2022-03-15 | 2022-06-24 | 浙江大学 | Silicon etching method |
| CN114792744A (en) * | 2022-05-07 | 2022-07-26 | 通威太阳能(眉山)有限公司 | Solar cell and preparation method and application thereof |
| CN218160392U (en) * | 2022-09-26 | 2022-12-27 | 滁州捷泰新能源科技有限公司 | Solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116177550A (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sailor et al. | Surface chemistry of luminescent silicon nanocrystallites | |
| Mangolini et al. | Plasma synthesis and liquid-phase surface passivation of brightly luminescent Si nanocrystals | |
| Kelly et al. | An investigation into near-UV hydrosilylation of freestanding silicon nanocrystals | |
| Clark et al. | From hydrogen silsesquioxane to functionalized silicon nanocrystals | |
| Thiessen et al. | Silicon nanoparticles: Are they crystalline from the core to the surface? | |
| Yu et al. | Room temperature hydrosilylation of silicon nanocrystals with bifunctional terminal alkenes | |
| US7371666B2 (en) | Process for producing luminescent silicon nanoparticles | |
| Carbonaro et al. | Carbon dots in water and mesoporous matrix: Chasing the origin of their photoluminescence | |
| Yang et al. | Radical initiated hydrosilylation on silicon nanocrystal surfaces: An evaluation of functional group tolerance and mechanistic study | |
| KR101331435B1 (en) | Method for preparing nanocrystalline silicon in SiO2 and freestanding silicon nanoparticles | |
| Martín-García et al. | Efficient charge transfer in solution-processed PbS quantum dot–reduced graphene oxide hybrid materials | |
| Ghosh et al. | Impact of anchoring monolayers on the enhancement of radiative recombination in light-emitting diodes based on silicon nanocrystals | |
| KR20130014529A (en) | Photoluminescent nanoparticles and method for preparation | |
| Li et al. | Aerosol-phase synthesis and processing of luminescent silicon nanocrystals | |
| JPWO2006025428A1 (en) | Visible light emitting material using surface modification of silica fine particles and method for producing the same | |
| WO2005016824A2 (en) | Synthesis of nanoparticles by an emulsion-gas contacting process | |
| Pereira et al. | Freestanding silicon nanocrystals with extremely low defect content | |
| CN116177550B (en) | Surface passivation method and application of silicon nano material | |
| Loh et al. | Photoluminescent Si/SiO2 Core/Shell Quantum Dots Prepared by High-Pressure Water Vapor Annealing for Solar Concentrators, Light-Emitting Devices, and Bioimaging | |
| Huang et al. | Regulating the fluorescence emission of CdSe quantum dots based on the surface ligand exchange with MAA | |
| CN107057691B (en) | A kind of preparation method of the colloidal state silicon nanocrystal of surface modification | |
| Caregnato et al. | Silanization effect on the photoluminescence characteristics of crystalline and amorphous silicon nanoparticles | |
| Wang et al. | Structural evolution and effective improvement of emission quantum yields for silicon nanocrystals synthesized by femtosecond laser ablation in HF-contained solution | |
| Xu et al. | A novel one-step synthesis of bright luminescent silicon nanocrystals capped with hydrophobic surface | |
| Gupta et al. | Enhanced long-term stability of functionalized silicon nanoparticles using esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |