CN101379222A - Germanium and germanium alloy nanoparticle and method for producing the same - Google Patents
Germanium and germanium alloy nanoparticle and method for producing the same Download PDFInfo
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- CN101379222A CN101379222A CN 200580020236 CN200580020236A CN101379222A CN 101379222 A CN101379222 A CN 101379222A CN 200580020236 CN200580020236 CN 200580020236 CN 200580020236 A CN200580020236 A CN 200580020236A CN 101379222 A CN101379222 A CN 101379222A
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910000927 Ge alloy Inorganic materials 0.000 title claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 50
- 238000005530 etching Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 5
- 239000012620 biological material Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 3
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- 238000000103 photoluminescence spectrum Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 12
- 239000005543 nano-size silicon particle Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 239000007788 liquid Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 206010058490 Hyperoxia Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- RBFDCQDDCJFGIK-UHFFFAOYSA-N arsenic germanium Chemical compound [Ge].[As] RBFDCQDDCJFGIK-UHFFFAOYSA-N 0.000 description 2
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- 239000002096 quantum dot Substances 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- 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
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/163—Solid materials characterised by a crystal matrix
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- H—ELECTRICITY
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- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/04—Processes or apparatus for excitation, e.g. pumping, e.g. by electron beams
- H01S5/041—Optical pumping
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- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/10—Construction or shape of the optical resonator, e.g. extended or external cavity, coupled cavities, bent-guide, varying width, thickness or composition of the active region
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/3027—IV compounds
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Abstract
In the invention, an electrochemical etching of crystalline germanium or a germanium alloy produces well-segregated chromatic clusters of nanoparticles. Distinct strong bands appear in the photoluminescence spectra under 350 nm excitation with the lowest peaks in wavelength identified to be at 430, 480, and 580 and 680-1100 nm. The material may be dispersed into a discrete set of luminescent nanoparticles of 1-3 nm in diameter, which may be prepared into colloids and reconstituted into films, crystals, etc.
Description
Technical field
Technical field of the present invention is a nano material.
Background technology
The nano silicon particles of diameter～1nm demonstrates stimulated emission.Block (bulk) silicon be indirect band gap be 1.1eV, direct band gap be 3.2eV to the insensitive indirect bandgap material of light.To have produced energy gap effectively be 3.55eV and have efficient optically active Wideband direct band gap material but diameter is the nano silicon particles of 1nm.The indirect band gap of 1nm nano silicon particles 1.1eV is equivalent to infrared region 1.1 mum wavelengths.We showed about the research work of 1nm nano silicon particles that it had medium emission activity at infrared region in the past.The 1nm nano silicon particles of prepared yardstick homogeneous in the more early stage work (having about thousandth or large-size still less) has the blue emission of feature.Referring to, people's such as Akcaki " Detection of luminescent single ultrasmall silicon nanoparticles usingfluctuation correlation spectroscopy " for example, Appl.Phys.Lett.76 (14), p.1857 (April 3,2000).Have hydrogen-or oxygen-end group, perhaps with nitrogen-, the functionalized nano silicon particles of carbon-key also is synthesized out.Work has in the past also prepared the nanoparticle of a series of size homogeneous (unique size of particles is in the 1-3nm scope), the very strong fluorescence of emission, and at other particles of infrared region emission.This series comprises 1nm (emission blue light), 1.67nm (transmitting green light), 2.15nm (emission gold-tinted), 2.9nm (red-emitting) and 3.7nm (emission infrared light).Referring to: people such as O.Belornoin " Observation of amagic discrete family of ultrabright Si nanoparticles; " Appl.Phys.Lett.80 (5), people's such as p841 (February 4,2002) and Nayfeh the disclosed patent application 20020070121 of the U.S..
Optical interconnection has a lot of application.An application example is the high-speed data communications that is used between server, no matter be cabinet to cabinet (cabinet-to-cabinet) or plate to plate (board-to-board) rank on.Another application is to be used for interconnecting on the chip level, utilizes III-V family system on the prior art, for example GaAs or InP-InGaGa PiN.It is because the favourable condition in their superior person's characters and the manufacturing that IV family material has special importance.For example, silicon class detector can be made with the silicon CMOS method of routine, and this method is compared with the manufacture method of III-V family, can realize with lower cost usually.
Conventional photo-detector of making in the compound semiconductor substrate and the combination of blocky silicon chip are in order to solve multicore sheet problem, and this is the comparison costliness.But, because silicon has big absorption length (20 μ m) at 820nm place, and abstinence absorption (forbidden absorption) is arranged, so blocky silica-based photo-detector has limited detection efficiency and wavelength region at 1300nm and 1500nm place.Arsenic germanium or gallium matrix tie up to 1300 and the 1500nm place absorption and sensitivity above bulk silicon are arranged.Arsenic germanium or gallium arsenide class system 1300 and the 1550nm place have better absorption and susceptibility than blocky silicon.
Nanoparticle based photodetector; be also referred to as the quantum dot light electric explorer; compare the chance that the increase photoelectric transformation efficiency is provided with big device, the degree of increase makes and can alleviate or eliminate the needs that use amplifying circuit in conventional system for the little photoelectric current that utilizes conventional bulk silicon detector assembly to produce.System based on Si, Ge and GeSi film of nanoparticles or quantum dot film is in the news recently, but efficient is general.The Ge class photodetector that for example utilizes the film that constitutes by big quantum substructure (50nm) to 820,1300 and the response of 1550nm wavelength be respectively 130,0.16 and 0.08mA/W.Referring to: for example, people such as B.C.Hsu " Highefficiency 820 nm MOS Ge quantum dotphotodetectors for short-reach integrated optical receivers with 1300 and 1550nm sensitivity; " IEDM, 91 (2002) (IEEE publication).The current-responsive of these levels is lower than the photoelectric device that use for short distance (short reach) photoelectricity communication provide required simple integrated those.Higher performance especially makes that in the higher performance at 820nm place it is feasible photoelectric device being integrated in the silicon chip that the short distance optical communication uses.
Summary of the invention
In the present invention, the chemical etching of crystal germanium or germanium alloy has produced and has separated the well colored cluster (chromatic clusters) of (well-segregated) nano particle.Occurred significantly strong bands of a spectrum in the luminescent spectrum under 350nm excites, and the ebb in the wavelength is confirmed to be positioned at 430,480 and 580, and the 680-1100nm place.The luminous nano granule that it is 1-3nm that described material can be dispersed into one group of discontinuous diameter, these nano particles can be prepared into colloid or structure film forming, crystal etc.
Description of drawings
Figure 1A and 1B show the luminescent spectrum of etching Ge wafer (wafer) under 365nm excites that obtains from the laboratory sample different piece.
Fig. 2 is presented at the luminescent spectrum of the Ge sample of the experiment of obtaining under the 365nm excitaton source at infrared region; With
Fig. 3 shows the FTIR spectrum of the Ge sample of experiment.
Implement best mode of the present invention
The present invention relates to germanium and germanium alloy nanoparticle, and the method for preparing them.The infrared emission of nano particle causes special interest in myriad applications.Can constitute the basis of sheet at the photodetector of infrared region efficient nano material type or phototransistor to sheet (chip-to-chip) and plate to the optical interconnection of plate (board-to-board).Compare with bulk silicon, block germanium has reduced indirect band gap (0.66 couple of 1.1eV) and direct band gap (0.9 couple of 3.2eV), and a kind of purposes of germanium nano particle of the present invention is that photosensitive response is extended to infrared region.
In the present invention, we adopt at chemical milling agent solution such as HF/H
2O
2/ H
2The method of chemical etching crystal germanium or germanium alloy among the O, the colored cluster of separating good nano particle with preparation, it shows extremely bright (ultrabright) blueness, green and yellow/orange under 365nmUV excites luminous, and very effective ir radiation.Therefore, the device of sensitive Si/Ge nano-particle material class can cover with near ultraviolet to infrared very wide wavelength region.A useful especially application in the infrared band significant response is to be used for infrared bio-imaging to use.
The method that produces the nano particle cluster of embodiment of the present invention is bipolar (bipolar) electrochemical treatment, and this method is included in extrinsic current and exists down with in block germanium or germanium alloy such as the wafer insertion chemical etching liquor.Germanium is taken on electrode in the chemical etching process.Another electrode also contacts chemical milling and bathes.During etching, with reversal of current.Wafer is advanced into gradually can be used for increasing the etching area in the bath.A kind of speed example is 1 millimeter of about per minute.When in this case, backing away (gradual retreat) at wafer with reversal of current.In addition, can after wafer is increased to its elemental height, implement the reverse of electric current, begin to advance gradually the second period of wafer then.
In a preferred embodiment of the invention, we adopt at HF/H
2O
2/ H
2The method of chemical etching crystal germanium in the etching solution of O and methyl alcohol.In another embodiment, used different etchant solutions, promptly moisture HCl/ methyl alcohol electrolysis bath of liquid.Etching process has produced the Ge nano particle of one deck uniform-dimension on the surface of block germanium.After etching, the Ge electrode that the surface is formed with the Ge nano particle separates with etchant solutions.Flushing has the Ge of nano grain surface then, removes whole etchant solutions.Particle can by paddling process as shake, impact, scraping or ultrasonic agitation (the preferred latter) remove from bulk material.Usually, all be suitable with any method of the surface isolation of the block Ge of nano particle and etching or Ge alloy, but the solvent of destructive force preferably is provided by ultrasonic wave.In ultra sonic bath,, therefore can use multiple solvent because particle is the hydrogen passivation.The example of solvent comprises acetone, alcohol, water and other organic solvents.In case separate, just can making ins all sorts of ways is shaped to colloid, crystal, film and other forms that needs with nano particle.Particle can also apply or mix.The method of describing in coating and adulterated method and the United States Patent (USP) 6,585,947 that is used for nano silicon particles is similar, but considers the chemical property difference of Ge, and applying the specified scheme of using may some difference.The end capped germanium particle of H-can be functionalized with alkynes.For example, containing 1,3 of 20%1-laurylene, the backflow several hrs causes adding the dodecyl of surface bonding in the 5-trimethylbenzene (v/v).It is thermoinducible germanium hydrogenation (hydrogermylation) reaction.
In another embodiment of the present invention, replace blocky germanium with silicon-germanium alloy.Implement chemical etching as discussed above, described alloy is dispersed into nano particle.Alloy can prepare by ion perfusion or molecular beam epitaxy (the molecular beam epitaxy) process of growing nonparasitically upon another plant.Germanium-silicon wafer that one embodiment example uses 20-80 (Ge-silicon) to form.For this ratio, the nanoparticle of diameter 1nm can have Si
24Ge
5Structure (24 Siliciumatoms and 5 Ge atoms).Perhaps we can use 80-20 (Ge-silicon) to form, and this composition obtains Ge
24Si
5(5 Siliciumatoms and 24 Ge atoms).The ratio of Ge and alloying element allows to adjust to be formed, and this makes that the wavelength response of alloy nanoparticle and doped nanoparticle obtains adjusting.Our theoretical modeling shows, can obtain several high-quality Si/Ge nano particle structures.
We have experimentized proves method of the present invention.In experiment, we use and have added hydrogen peroxide (H
2O
2) moisture HF/ methyl alcohol electrolysis bath of liquid prepare sample.Used germanium sample be (100) orientation, resistivity be 1-10ohm-cm (ohm. centimetre), it is the Ge wafer of P-type doped with boron.In addition, the organic class impurity in the superoxide clean wafers of HF hyperoxia voltinism with hydrogen end-blocking Ge obtains high-quality nanostructure.Etching reagent example in experiment is 0.5mL, 0.45mL and 0.4mL, and promptly volume ratio is approximately HF, the H of 1:1:1
2O
2And methanol mixture.(assumed density is 350mA/cm at anodizing electric current 180mA
2) descended this wafer of etching 5 minutes.Anodized last, the polarity of counter-rotating electrode was carried out the negative electrode etch step 2 minutes.
In experiment, obtained separating good colored cluster, it excites down at 365nm UV, and it is luminous to show extremely bright blueness, green and yellow/orange, and very effective ir radiation.HF and H
2The oxide compound reaction of O both and Ge, the superoxide that therefore adds the hyperoxia voltinism has improved etch-rate, obtains much smaller nanostructure.But the preparation of (spatially resolved) colored cluster of spatial discrimination is consistent with the size-dependent quantum limit (quantum confinement) of radiative recombination (radiative recombination) in the Ge nanostructure.
We use the radiation from Hg lamp (being incident in the substrate usually) to obtain luminescent image.At the target place, adopt the object lens of 0.6NA, the power of 1-15mW is accumulated on the site of 0.5mm diameter, the intensity that obtains is 0.13-2W/cm
2In the other direction surveying luminous and by (3CCD) carrying out record based on rgb filter/prismatical chromatic dispersion charge coupled device (dispersive charge coupled device).The scattering of specific cut-off filter elimination incident light wave strong point is also removed background.Excite down at 365nm, we observe the luminous cluster of blueness, green and yellow/orange.
We can prepare blueness under higher etching current condition be main sample.These samples belong to 1nm Ge particle clusters.When exciting under 365nm excites, it is the luminous of master by the blue-light-emitting cluster mainly that the sample for preparing under higher etching conduction of current shows, and other colors are considerably less.
Analyzing spectrographic with the optical multichannel that disposes the prism dispersion element (multichannel) analyser distributes.Figure 1A and 1B have provided resulting spectrum.When light beam rested on blue cluster, photoluminescent band peaked at 425nm.The rapid rising of the blue edge of bands of a spectrum is caused by cut-off filter.When light beam rested on green/yellow site, emission band peaked at 490nm.Under many circumstances, may there be yellow acromion (shoulder) at the 580nm place.
In order to survey infrared active, we use fiber spectrometer, and it comprises that transmission excites and obtain the optical fiber of emission.We use holographic grating, and it is the polymer replication grating of prototype grating.It is the near infrared grating, and cutting (groove) density is 600/mm, and blaze angle is 1 μ m, and optimum efficiency is in the 0.65-1.1 mu m range.Other passages use the UV-VIS holographic grating, and cutting density is 600/mm, and blaze wavelength is 0.4 μ m, and optimum efficiency is in the 0.25-0.80 mu m range.The decay of near infrared (NIR) optical fiber is almost 50db/km.In interested 900-1000nm zone, transmissivity is～90%.
Fig. 2 has shown the infrared spectra that obtains under the excitaton source of 365nm.(680-1100nm) has photoluminescent band at dark heat.The lines shape of infrared band is asymmetric, sharply rises at the 680nm place, and slowly falls, and just in time falls into～infrared part at 1100nm place.Proofread and correct the efficient of infrared eye and measurement is averaged, the result shows that infrared emission is than the strong twice of VISIBLE LIGHT EMISSION.
In order to determine whether any oxidizing reaction has taken place in the chemical etching process, we have measured 500-4500cm
-1Infrared absorption in the scope.In air, use ATI-Mattson Galaxy modelGL-5020 to obtain fourier-transform infrared (FTIR) data.Result shown in Figure 3 shows at 830-880cm
-1There is absorption at the place, and this is owing to the beam mode of bonded hydrogen on the Ge crystallite surface.The signal of germanium substrate is removed from data.These data also are presented at 550-600cm
-1There is absorption at the place because of the vibration modes of the hydrogen of swing.On the other hand, we do not see that expection appears at 900-1100cm
-1The signal of oxygen in the zone shows the degree height of hydrogen passivation.Therefore, can not be based on oxide compound from our emission of sample.In fact, the dissolution rate of oxide compound is all more faster than any common oxidising process in the aqueous solution.
Luminous can the explanation in nanostructure according to quantum limit.The lattice parameter of Si and Ge is suitable, and Ge goes out 5% greatly.Therefore, the spherical stripping and slicing of 1nm diameter obtains the cluster Ge that is made up of 29 germanium atoms in block Ge
29Identical stripping and slicing also obtains the cluster (Si of 29 Siliciumatoms in Si
29).The method for preparing a series of discontinuous nano silicon particles comprises 1,1.67,2.15,2.85 and the 3.7nm particle diameter.Referring to " Observation of a magic discretefamily of ultrabright Sinanoparticles, " Appl.Phys.Lett.80 (5) of people such as Belomoin, p 841 (February 4,2002); And U.S.'s publication application 20020070121 of people such as Nayfeh.Based on the size difference between Si and the Ge, the corresponding size of Ge nano particle is 1,1.75,2.25,3.0 and 3.9nm.
There is significant difference at dark heat Si and Ge.The nano silicon particles of different size provides and is positioned at the luminous of 1160-1300nm band-edge, and efficient is 6% of visible region emission.The germanium nanoparticle provides luminous in the 680-1100nm scope, and efficient and visible region emission are quite or bigger than the efficient of visible region emission.Germanium also is desirably in 1, and 500-3 causes luminous in the 000nm scope.Among the Ge strong emission extend to infrared region be because blocky Ge than the band gap low ((0.66 pair of 1.1eV indirect band gap) and (0.9 pair of 3.2eV direct band gap)) of Si.Based on the activity of visible region, observed emission band (their peak position is in blue, green and yellow light area) is seen the important minor structure system of 1-3nm Ge nano particle (substructure regime) that derives from.Method preparation size of the present invention is at the Ge and the Ge-alloy nanoparticle of～1-3nm scope.
In another embodiment, we use and contain small amount of H
2O
2Moisture HCl/ methyl alcohol electrolysis bath of liquid.Seal the Teflon cylindrical chamber in the bottom with wafer.The back side of metal sheet and wafer electrically contacts.Charge into etching solution in the cylindrical chamber.Etching reagent is HCl and the methanol mixture of 1:1.Platinum wire electrode is immersed in the etching reagent, be positioned at certain altitude place (for example 2cm), substrate top, perpendicular to substrate.When anode was taken in the germanium substrate, platinum filament was taken on negative electrode, with wafer suitable etching with the anodizing current density (for example～230mA/cm
2) down anodizing 5 minutes.Last in this anodizing step with the reversal of poles of electrode, carries out negative electrode step 2 minute.Remove etching reagent then, water flushing wafer is then with acetone rinsing and dry for some time.Observe the spectrum of similar particle cluster, but it is askew to the orange/red size to distribute.
In another embodiment, we find that we can be by adding Ge salt (as GeCl in etching reagent
4) solution improves the formation of nano particle and increase productive rate.In addition, we also improve formation by add granular Ge in etching reagent, the Ge wafer of this granular Ge for pulverizing.
Although shown and described specific embodiments of the present invention, it should be understood that for the person of ordinary skill of the art other changes, to substitute and select all be conspicuous.Can carry out these changes, substitutes and select and do not depart from by the definite the spirit and scope of the present invention of appended claims.
In appended claims, illustrated various feature of the present invention.
Claims (28)
1. the method for preparing elemental Germanium or germanium alloy nanoparticle, this method may further comprise the steps:
Germanium or germanium alloy electrode are contacted with etchant solutions;
By between germanium or germanium alloy electrode and another electrode, applying voltage to the surface of germanium or germanium alloy electrode supply electric current;
Reversal voltage also repeats described supply step;
Germanium or germanium alloy electrode are separated with etchant solutions.
2. the method for claim 1, it also comprises step:
With germanium or germanium alloy nanoparticle and germanium or germanium alloy electrode separation.
3. the method for claim 2 wherein saidly comprises germanium or germanium alloy nanoparticle separation steps:
Make germanium or germanium alloy electrode bear strength, so that with germanium or germanium alloy nanoparticle and germanium or germanium alloy electrode separation.
4. the method for claim 3 is wherein provided by ultrasonic wave in described strength of bearing in the step.
5. the method for claim 2 wherein saidly comprises germanium or germanium alloy nanoparticle separation steps:
Germanium or germanium alloy electrode placed solvent and make germanium or the germanium alloy electrode bears strength, so that with germanium or germanium alloy nanoparticle and germanium or germanium alloy electrode separation.
6. the method for claim 5, its also be included in after the described separating step and described germanium or germanium alloy electrode are placed the solvent solution step before the step of flushing germanium or germanium alloy electrode.
7. the process of claim 1 wherein that described contact procedure comprises advances germanium or germanium alloy in the etchant solutions gradually.
8. the method for claim 1, it also comprises the step of doped germanium or germanium alloy nanoparticle.
9. the method for claim 1, it also comprises the step that applies germanium or germanium alloy nanoparticle.
10. the method for claim 9, wherein said coating step comprise with biomaterial and apply described particle.
11. the process of claim 1 wherein that described another electrode is formed by platinum, and germanium or germanium alloy electrode comprise monocrystalline germanium.
12. the process of claim 1 wherein that germanium or germanium alloy electrode comprise the germanium of p-type doped with boron.
13. the process of claim 1 wherein that etchant solutions comprises HF/H
2O
2/ H
2O and methyl alcohol.
14. the method for claim 13, wherein etchant solutions also comprises the Ge salts solution.
15. the method for claim 13, wherein etchant solutions also comprises granular germanium.
16. the process of claim 1 wherein that etchant solutions comprises HCl and methyl alcohol.
17. the method for claim 16, wherein etchant solutions also comprises the Ge salts solution.
18. the method for claim 16, wherein etchant solutions also comprises granular germanium.
19. prepare the method for elemental Germanium or germanium alloy nanoparticle, this method may further comprise the steps:
Block germanium is contacted with the chemical milling agent solution;
The bipolar electrochemical etching should bulk germanium during described contact procedure; And
Germanium or germanium alloy electrode are separated with etchant solutions.
20. the method for claim 19, wherein said contact procedure comprise germanium or germanium alloy are advanced in the etchant solutions gradually.
21. the method for claim 19, wherein etchant solutions comprises HF/H
2O
2/ H
2O and methyl alcohol.
22. the method for claim 21, wherein etchant solutions also comprises the Ge salts solution.
23. the method for claim 21, wherein etchant solutions also comprises granular germanium.
24. the method for claim 19, wherein etchant solutions comprises HCl and methyl alcohol.
25. the method for claim 24, wherein etchant solutions also comprises the Ge salts solution.
26. the method for claim 24, wherein etchant solutions also comprises granular germanium.
27. the elemental Germanium material, it comprises the nano particle of size in～1-3nm scope.
28. Ge alloy material, it comprises the nano particle of size in～1-3nm scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/849,536 | 2004-05-19 | ||
| US10/849,536 US20050072679A1 (en) | 1999-10-22 | 2004-05-19 | Germanium and germanium alloy nanoparticle and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101379222A true CN101379222A (en) | 2009-03-04 |
Family
ID=37667920
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|---|---|---|---|
| CN 200580020236 Pending CN101379222A (en) | 2004-05-19 | 2005-05-16 | Germanium and germanium alloy nanoparticle and method for producing the same |
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| Country | Link |
|---|---|
| EP (1) | EP1756335A4 (en) |
| JP (1) | JP2008504448A (en) |
| CN (1) | CN101379222A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN106400058A (en) * | 2016-09-14 | 2017-02-15 | 闽南师范大学 | Preparing method for water-soluble germanium nano particles |
| CN107217279A (en) * | 2017-05-31 | 2017-09-29 | 东北大学 | A kind of method that electrolysis prepares metal nanoparticle |
| CN108411267A (en) * | 2018-04-25 | 2018-08-17 | 河南科技大学 | A method of preparing free state polyhedron Ag nano particles |
| CN109585504A (en) * | 2018-10-08 | 2019-04-05 | 惠科股份有限公司 | Display panel and manufacturing method thereof |
| WO2020119537A1 (en) * | 2018-12-11 | 2020-06-18 | 惠科股份有限公司 | Photoreceptor, panel, and manufacturing method for photoreceptor |
-
2005
- 2005-05-16 JP JP2007527339A patent/JP2008504448A/en active Pending
- 2005-05-16 CN CN 200580020236 patent/CN101379222A/en active Pending
- 2005-05-16 EP EP05785299A patent/EP1756335A4/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN106400058A (en) * | 2016-09-14 | 2017-02-15 | 闽南师范大学 | Preparing method for water-soluble germanium nano particles |
| CN106400058B (en) * | 2016-09-14 | 2018-05-29 | 闽南师范大学 | A kind of preparation method of water solubility germanium nano-particle |
| CN107217279A (en) * | 2017-05-31 | 2017-09-29 | 东北大学 | A kind of method that electrolysis prepares metal nanoparticle |
| CN107217279B (en) * | 2017-05-31 | 2018-10-02 | 东北大学 | A kind of method that electrolysis prepares metal nanoparticle |
| CN108411267A (en) * | 2018-04-25 | 2018-08-17 | 河南科技大学 | A method of preparing free state polyhedron Ag nano particles |
| CN109585504A (en) * | 2018-10-08 | 2019-04-05 | 惠科股份有限公司 | Display panel and manufacturing method thereof |
| US11367847B2 (en) | 2018-10-08 | 2022-06-21 | HKC Corporation Limited | Display panel, display device and manufacturing method |
| WO2020119537A1 (en) * | 2018-12-11 | 2020-06-18 | 惠科股份有限公司 | Photoreceptor, panel, and manufacturing method for photoreceptor |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1756335A4 (en) | 2008-08-27 |
| JP2008504448A (en) | 2008-02-14 |
| EP1756335A2 (en) | 2007-02-28 |
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