CN1804122A - Transplantable ultrathin nano-porous gold film and method for preparing the same - Google Patents
Transplantable ultrathin nano-porous gold film and method for preparing the same Download PDFInfo
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- CN1804122A CN1804122A CN 200510111258 CN200510111258A CN1804122A CN 1804122 A CN1804122 A CN 1804122A CN 200510111258 CN200510111258 CN 200510111258 CN 200510111258 A CN200510111258 A CN 200510111258A CN 1804122 A CN1804122 A CN 1804122A
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Abstract
The preparation method for transplantable ultrathin nano porous gold film comprises: preparing Au-Cu alloy with vacuum evaporation method, thermal annealing, and removing alloy with acidic solution. This product can be used in catalysis, bio-sense, porous electrode and other fields as well as nano grating and non-linear optics fields for special optical and high light transmission features
Description
Technical field
The invention belongs to nano material and thin-film material technical field, be specifically related to a kind of transplantable ultrathin nano-porous gold film and preparation method thereof.
Technical background
Nano material is obviously different with traditional continuous solid body material, because nanometer size effect and big specific surface area effect, this class material can show special physicochemical character, comprises special photoelectric functional character, transport property and mechanical property.Nano material has various ways, such as the film of nanoparticle, nanometer rod, nano wire, nano thickness and nano-solid (nanophase) material etc.The definition of nano material is mainly based on scale effect, so nano material can be the entity of nanoscale, also can be the space of nanoscale.
The porous precious metal material is good owing to chemical stability, and has been widely used in fields such as catalysis, bio-sensing, porous electrode, energy storage, microfluidic control and transmission mediums, has been subjected to paying close attention to widely.This class material can prepare with simple removal alloying method.([1]Jonah?Erlebacher，Michael?J.Aziz，Alain?Karma，et?al.Evolution?ofnanoporosity?in?dealloying.Nature，2001，410：450-453.[2]Yi?Ding，Jonah?Erlebacher.Nanoporous?metals?with?controlled?multimodal?pore?size?distribution.J?Am?Chem?Soc，2003，125：7772-7773.)
In recent years, because the metal nano-void film is found and has special optical property and light percolating property, caused worldwide extensive concern.But the preparation of uniform nano-porous metallic film is very difficult, adopts such as needs to form porous metal film by depositing noble metal on original template, is difficult to produce in batches.([3]T?W?Ebbesen，H?J?Lezec，H?FGhaemi，et?al.Extraordinary?optical?transmission?through?sub-wavelength?hole?arrays[J].Nature，1998，391：667-669；[4]Hui?Xu，Werner?A?Goedel.Preparation?of?ultrathinfree-standing?porous?metal?films.Small，2005，1：808-812.)
In view of the widespread use value of nano-hole golden film, press for a kind of simple and convenient preparation method of development and satisfy scientific research and commercial demand this class thin-film material.
Summary of the invention
The objective of the invention is to propose the golden film in a kind of ultrathin nanometer hole transplantable, self-supporting, and propose the simple and convenient process for preparing of this nano-hole golden film:
The transplantable ultrathin nano-porous gold film that the present invention proposes, its thickness is 50～200 nanometers, has equally distributed nano aperture in the film.Usually this hole aperture is 30-150nm, specifically can be regulated by CONTROL PROCESS.This film is a self-supporting, can preserve standby in the aqueous solution; Can also transfer on other solid surface, and become to sprawl state.This film obtains through acid corrosion by thermal anneal process Au-Cu alloy firm again.
The preparation method of above-mentioned film is as follows: the sheet mica that adopts fresh cleavage is as substrate, and the mixture of vacuum thermal evaporation Au and Cu obtains the alloy firm of Au and Cu.Then, the alloy firm sample is put into baking oven, under the temperature of setting, the thermal treatment of in atmospheric atmosphere, annealing.Afterwards, film is immersed removal alloying in the acid solution that configures, to remove copper oxide and Cu wherein.Simultaneously, gold thin film can be peeled off from mica substrate, becomes the golden film of self-supporting in water.Clean golden membrane sample repeatedly with deionized water.At last, be kept in the deionized water golden membrane sample standby.
In above-mentioned production process, during vacuum evaporation, Au and Cu amount ratio are 0.2～5 (calculating by the atomicity ratio).If it is x that golden consumption accounts for the atomic percent of total metal consumption, the alloy composition that makes is Au
xCu
1-x.
In above-mentioned preparation procedure, the thermal annealing temperature range of setting is 150～300 ℃, and the thermal annealing time is 2～48 hours.
In above-mentioned preparation procedure, the acid solution that is used for removal alloying can adopt hydrochloric acid, sulfuric acid, nitric acid or acetic acid etc.The concentration of acid is 0.001～1mol/L.
In above-mentioned preparation procedure, the thickness of golden film can be by the sedimentary amount control of vacuum thermal evaporation, and may command prepares the arbitrary numerical value of thickness in 50～200nm scope, such as the thick gold nano hole film of 80nm.Also has equally distributed nanometer hole in the film.
In above-mentioned preparation procedure, the area size of golden film is by the size and the decision of removal alloying process of mask, and the area size can be 0.1mm
2～10cm
2Arbitrary numerical value in the scope is such as 0.5cm
2Perhaps 4cm
2
The self-supporting nanometer hole gold film that the present invention proposes can move on on other solid surfaces from Transfer in Aqueous Solution, and becomes to sprawl state.This transplantable, self-supporting, ultrathin nanometer hole gold film can have using value in extensive fields, comprise fields such as catalytic field, bio-sensing field, porous electrode field, energy storage field, microfluidic control and transmission medium.This gold film can be used as the metal medium of nanometer grating and high printing opacity.
Further the nano-hole golden film that the present invention makes is also found in measurement, also has special optical characteristics and optical transmission characteristics, therefore in non-linear optical field, nanometer grating and near field optic field significant application value is arranged.
Description of drawings
Fig. 1 is from Au
0.5Cu
0.5The SEM image of the golden film that obtains.
Fig. 2 is from Au
0.36Cu
0.64The image of the golden film that obtains.Wherein, (a) being in a big way SEM image, (b) is the SEM image under the high-resolution.
Fig. 3 is surface enhanced Raman scattering (SERS) analytical results.Wherein, (a) be from Au
0.36Cu
0.64The analytical results of the golden film that obtains (b) is the analytical results that is deposited on the proof gold film of mica surface.
Embodiment
The ultrathin nanometer hole gold film that the invention is further illustrated by the following examples proposes
The sheet mica that utilizes fresh cleavage is as substrate, 4 * 10
-3Under the vacuum tightness of Pa, the Au of proportioning and the mixture (Au of Cu are set in vacuum evaporation
xCu
1-x).The thickness of alloy firm utilizes the quartz (controlled) oscillator monitoring.Then, sample is put into baking oven, under 200 ℃ temperature, annealed 25 hours in the air atmosphere.Afterwards, the dilute hydrochloric acid that film is immersed 0.1mol/L carries out corrosion treatment, to remove Cu oxide compound and the unoxidized nanometer Cu in the film.In using the process of hcl corrosion, gold thin film can spontaneously be peeled off from mica substrate, and what the gold thin film sample area that peels off was bigger can reach 4cm
2About.Sample is cleaned repeatedly with deionized water, remove the resultant of reaction and other impurity that are adsorbed on film surface.At last, be kept in the deionized water standby.
Scanning electronic microscope (SEM) is observed and is confirmed that this golden film does not have breakage, and flexible collapsible, the planarization of gold thin film is better, and thickness can be controlled at below 100 nanometers, also has intensive nano aperture in the film.
Fig. 1 is Au
0.5Cu
0.5The golden membrane sample that alloy film obtains with the corrosion of 0.1mol/L dilute hydrochloric acid, SEM image show that there is nano aperture relatively uniformly in this film.
Fig. 2 is Au
0.36Cu
0.64The golden membrane sample that alloy film obtains with the corrosion of 0.1mol/L dilute hydrochloric acid.Wherein, Fig. 2 (a) is a SEM image in a big way; Fig. 2 (b) is the SEM image under the high-resolution, demonstrates clear intensive nano aperture.
Fig. 3 is surface enhanced Raman scattering (SERS) analytical results.Wherein, Fig. 3 (a) is Au
0.36Cu
0.64Alloy film shows that with the golden membrane sample that the corrosion of 0.1mol/L dilute hydrochloric acid obtains this sample is at 50-220cm
-1Scope has very strong enhancing peak, and it is relevant with the surperficial drawn game area plasma that exists in the nano-porous thin film that this result estimates; Fig. 3 (b) is for being deposited on the proof gold film on the mica surface, the golden membrane sample of the continuous formation that obtains after process is peeled off.
Above-mentioned preparation process, in the scope of aforementioned correlation parameter, change correlation parameter, comprise annealing temperature (for example 150 ℃, 250 ℃, 180 ℃ etc.), annealing time (for example 2 hours, 45 hours, 20 hours etc.), the concentration of acid (0.01mol/L for example, 0.5mol/L, 0.8mol/L etc.), the type (for example sulfuric acid, nitric acid, acetic acid etc.) of acid, all can obtain Fig. 1-result shown in Figure 3, specifically be omitted.
Claims (9)
1, a kind of transplantable ultrathin nano-porous gold film is characterized in that the thickness of this film is 50～200 nanometers, has equally distributed nano aperture in the film.
2, the golden film in ultrathin nanometer hole according to claim 1 is characterized in that this film is a self-supporting, can preserve standby in the aqueous solution; Can also transfer on other solid surface, and become to sprawl state.
3, according to claim 1 and 2 described ultrathin nanometer holes gold film, it is characterized in that this film by thermal anneal process Au-Cu alloy firm, obtains through acid corrosion again.
4, the preparation method of the golden film in ultrathin nanometer hole according to claim 1, it is characterized in that: the sheet mica that adopts fresh cleavage is as substrate, and the mixture of vacuum thermal evaporation Au and Cu obtains the Au-Cu alloy firm; Then, the alloy firm sample is put into baking oven, under the temperature of setting, in atmospheric atmosphere, carry out anneal; Afterwards, film is immersed removal alloying in the acid solution that configures, to remove copper oxide and Cu wherein; Simultaneously, gold thin film can be peeled off from mica substrate, becomes the golden film of self-supporting in water.
5, the preparation method of the golden film in ultrathin nanometer hole according to claim 4, it is characterized in that: Au and Cu consumption count 0.2～5 by the atomicity ratio during vacuum thermal evaporation.
6, the preparation method of the golden film in ultrathin nanometer hole according to claim 4, it is characterized in that: the thermal annealing temperature is 150～300 ℃; The thermal annealing time is 2～48 hours.
7, the preparation method of the golden film in ultrathin nanometer hole according to claim 4, it is characterized in that: the acid solution that is used for removal alloying adopts hydrochloric acid, sulfuric acid, nitric acid or acetic acid, and the concentration of acid is 0.001～1mol/L.
8, as the application of the described ultrathin nanometer of one of claim 1～3 hole gold film in catalysis, bio-sensing, porous electrode, energy storage, microfluidic control and transmission medium.
9, as of the application of the described ultrathin nanometer of one of claim 1～3 hole gold film as the metal medium of nanometer grating and high printing opacity, and the application in nonlinear optics and near field optics.
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| CN101225515B (en) * | 2007-10-17 | 2010-10-06 | 哈尔滨工业大学（威海） | Method for preparing gold-nano array electrode |
| CN102644050A (en) * | 2012-04-16 | 2012-08-22 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN103272487A (en) * | 2013-03-13 | 2013-09-04 | 复旦大学 | Method for preparing nano-porous gold film through treating graphene as template |
| CN103936054A (en) * | 2014-04-22 | 2014-07-23 | 天津大学 | Synthesis method for copper sulphide powder with bicontinuous nano porous structure |
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| CN104628028A (en) * | 2014-12-19 | 2015-05-20 | 天津大学 | Method for preparing nanosheet cluster-structure cupric sulfide from titanium-copper amorphous alloy and application thereof |
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| CN106868536A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The Carbon dioxide electrochemical reduction preparation of porous copper electrode and its electrode and application |
| CN106995914A (en) * | 2017-05-24 | 2017-08-01 | 山东大学 | A kind of method for preparing self-supporting porous metal film |
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2005
- 2005-12-08 CN CNB200510111258XA patent/CN100557083C/en not_active Expired - Fee Related
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| CN101225515B (en) * | 2007-10-17 | 2010-10-06 | 哈尔滨工业大学（威海） | Method for preparing gold-nano array electrode |
| CN102644050A (en) * | 2012-04-16 | 2012-08-22 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN102644050B (en) * | 2012-04-16 | 2014-01-08 | 西安理工大学 | Method for preparing porous AlN/GaN film |
| CN103272487A (en) * | 2013-03-13 | 2013-09-04 | 复旦大学 | Method for preparing nano-porous gold film through treating graphene as template |
| CN104046953A (en) * | 2013-03-14 | 2014-09-17 | 河南大学 | Preparation method for APTES porous hydrophobic film |
| CN103936054A (en) * | 2014-04-22 | 2014-07-23 | 天津大学 | Synthesis method for copper sulphide powder with bicontinuous nano porous structure |
| CN103936054B (en) * | 2014-04-22 | 2015-08-26 | 天津大学 | A kind of synthetic method with the cupric sulfide powder of co-continuous nano-porous structure |
| CN104628028A (en) * | 2014-12-19 | 2015-05-20 | 天津大学 | Method for preparing nanosheet cluster-structure cupric sulfide from titanium-copper amorphous alloy and application thereof |
| CN104857956A (en) * | 2015-04-08 | 2015-08-26 | 北京科技大学 | Preparation method of Au catalyst for preparing KA oil |
| CN104992985A (en) * | 2015-07-07 | 2015-10-21 | 深圳市华星光电技术有限公司 | Thin film transistor and manufacturing method thereof, and array substrate |
| US9917208B2 (en) | 2015-07-07 | 2018-03-13 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Thin film transistor and method for manufacturing the same, and array substrate |
| CN104992985B (en) * | 2015-07-07 | 2018-08-21 | 深圳市华星光电技术有限公司 | Thin film transistor (TFT) and its manufacturing method, array substrate |
| CN105177502A (en) * | 2015-08-13 | 2015-12-23 | 西安交通大学 | Ultra-smooth metal film surface preparation method |
| CN105177502B (en) * | 2015-08-13 | 2017-12-15 | 西安交通大学 | A kind of preparation method of ultra-smooth metal film surfaces |
| CN106868536A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The Carbon dioxide electrochemical reduction preparation of porous copper electrode and its electrode and application |
| CN106847550A (en) * | 2017-02-15 | 2017-06-13 | 哈尔滨工业大学深圳研究生院 | A kind of laser boring template electroplates porous metal film and its method and application |
| CN106847550B (en) * | 2017-02-15 | 2018-10-09 | 哈尔滨工业大学深圳研究生院 | A kind of laser boring template plating porous metal film and its method and application |
| CN106995914A (en) * | 2017-05-24 | 2017-08-01 | 山东大学 | A kind of method for preparing self-supporting porous metal film |
| CN110066979A (en) * | 2019-05-27 | 2019-07-30 | 国家纳米科学中心 | A kind of raising gold nanoparticle film electro-catalysis reduction CO2Method of performance and products thereof |
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