CN1075842C - Process for generating metallic atom cluster smaller than 10 nm or sequential 2D dot-matrix of metallic atoms on single-molecular film - Google Patents
Process for generating metallic atom cluster smaller than 10 nm or sequential 2D dot-matrix of metallic atoms on single-molecular film Download PDFInfo
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- CN1075842C CN1075842C CN98103527A CN98103527A CN1075842C CN 1075842 C CN1075842 C CN 1075842C CN 98103527 A CN98103527 A CN 98103527A CN 98103527 A CN98103527 A CN 98103527A CN 1075842 C CN1075842 C CN 1075842C
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Abstract
The present invention belongs to the technological field of metal material with a two-dimensional ordered structure and particularly relates to a method for forming a two-dimensional ordered lattice of metal atom clusters or metal atoms which are smaller than 10 nm on a monomolecular film. Monodisperse two-dimensional ordered lattices of metal atom clusters or metal atoms are prepared by a single-tank method or three-tank method, and a polymerized film or a film formed in the aqueous solution of metal salts or metal salt complexes of 5*10<-6>M to 5* 10<-4>M is reduced in the aqueous solution of a reducing agent or is reduced by that the film absorbs metallic ions when the aqueous solution of a reducing agent contains the metal salts or metal salt complexes; a monomolecular film is transferred to a glass slide by a horizontal crystal pulling method or vertical crystal pulling method, and metal atoms and metal atom clusters which are smaller than 10 nm are respectively prepared. The obtained two-dimensional ordered lattice of metal atoms is a planar right-angle lattice.
Description
The invention belongs to metallic substance technical field, particularly relate to the method that on unimolecular film, forms less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms with two dimensional structure.
Metallic substance with nanostructure or ultra micro ordered structure because of performances such as its distinctive chemistry, optics, electronics, is widely used in every field by people.Especially " gold " that has two dimensional structure except having the important role, also because of the special avidity of itself and biomacromolecule, has special meaning to structure and the function of research biomacromolecule itself in the nano electron device in future.Yet at nano level, even on the atom level level, the two dimensional structure of metal is difficult to obtain.Existing method generally adopts airless injection to obtain incomplete metal monoatomic layer [EricGanz, Klaus Sattler, and John Clarke, Phys.Rev.Lett., 58,1856 (1988)].Because the atomicity of spraying is difficult to accurately control, and formed two-dimensional crystal lattice extremely unstable (only clock) in a measure, this method is difficult to be extended to a kind of preparation means of effective practicality.
The objective of the invention is to overcome the sequential 2 D crystalline network instability of the metal that prior art for preparing goes out, the method that forms on unimolecular film under a kind of room temperature less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms is provided.The metal atomic cluster that technical scheme of the present invention obtained is below 10 nanometers, and metal atomic cluster or sequential 2 D dot-matrix of metallic atoms are the flat square lattices.Can stablize under the lattice room temperature and reach more than 48 hours, simultaneously, when being the basis,,, can realize atomic ordered dot matrix truly as metallic gold for some metal with the LB film, rather than the monoatomic layer roughly on the statistical significance.
Technical scheme of the present invention is achieved in that
Based on the unimolecular film technology, obtain to be fixed on stable atoms metal two-dimentional structure on the unimolecular film by the chemical process on the unimolecular film.The used chemical process of the present invention is adsorption process, part desorption process and the reduction process that the ion of (containing) metal carries out on unimolecular film successively.Wherein in adsorption process, metal ion (Cu
2+, Ag
+) or the ion (AuCl of containing metal complex compound
4 -, PtCl
6 2-) be added into end liquid, under electrostatic force, adsorbed by the substrate unimolecular film, in the part desorption process, having adsorbed ionic substrate unimolecular film is placed in the pure water atmosphere, make the ion desorption of loose bonded non-specific adsorption, only stay specificity bonded adsorbed close layer, then in reduction process, the unimolecular film that more than has the adsorption of metal ions layer is placed in the reductive agent aqueous solution, is reduced into to be atoms metal or cluster.
1. the two-dimentional structure of single channel process system atoms metal
In standard unimolecular film groove, with the pure water is end liquid, spread in the groove being dissolved in the amphiphilic polymer in the chloroform or the unimolecular film of straight chain fatty acid or aliphatic amide (n=12～22), then unimolecular film is depressed into constant pressure, behind the balance certain hour, amphiphilic polymer need be used the UV-irradiation polymerization, or directly spreads the good film of polymerization, injects a certain amount of 5 * 10 then in end liquid
-6M to 5 * 10
-4The aqueous solution of M metal-salt or metal salt complex, the concentration that makes the metal ion in the end liquid is 5 * 10
-6M to 5 * 10
-4M; Through after the certain hour, with horizontal crystal pulling method or vertical crystal pulling method polymeric film is transferred on the hydrophobic slide glass, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-6To 10
-4Reduce in the reductive agent aqueous solution of M, at last slide glass is cleaned, nitrogen dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal atoms on unimolecular film.
2. the two-dimentional structure of three-flute legal system atoms metal
In three grooves of " three slot types " membrane instrument, in first groove, add 5 * 10
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex add pure water in second groove, add 5 * 10 in the three-flute
-7M to 5 * 10
-4The reductive agent aqueous solution of M, after the unimolecular film that is dissolved in amphiphilic polymer in the chloroform or straight chain fatty acid or aliphatic amide (n=12～22) spread over first groove, amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, under constant surface pressure, this polymeric film carefully is pushed into then in second cell body that is full of pure water, after leaving standstill, the last metal ion reduction that is pushed into the 3rd cell body with absorption again, after the reduction, with horizontal crystal pulling method or vertical crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal atoms on unimolecular film.
3. three-pit system prepares the two-dimentional structure of monodispersed metal atomic cluster
In three grooves of " three slot types " membrane instrument, in first groove, add 5 * 10
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex add pure water in second groove, add 5 * 10 in the three-flute
-7M to 5 * 10
-4The reductive agent aqueous solution and 5 * 10 of M
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex, after the unimolecular film that is dissolved in amphiphilic polymer in the chloroform or straight chain fatty acid or aliphatic amide (n=12～22) spread over first groove, amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, under constant surface pressure, this polymeric film is pushed in second cell body that is full of pure water, after leaving standstill, be pushed into of the metal ion reduction of the 3rd cell body again with absorption, after the reduction, with horizontal crystal pulling method or vertical crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal clusters on unimolecular film.
4. single channel process prepares the two-dimentional structure of monodispersed metal atomic cluster
In standard unimolecular film groove, with 5 * 10
-6M to 5 * 10
-4The aqueous solution of M metal-salt or metal salt complex is end liquid, spread in the groove being dissolved in the amphiphilic polymer in the chloroform or the unimolecular film of straight chain fatty acid or aliphatic amide (n=12～22), amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, then unimolecular film is depressed into constant pressure, after the balance, unimolecular film is transferred on the hydrophobic slide glass with horizontal crystal pulling method or vertical crystal pulling method, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-7To 10
-4The reductive agent aqueous solution and 5 * 10 of M
-6M to 5 * 10
-4In the aqueous solution of M metal-salt or metal salt complex, after the reduction, at last slide glass is cleaned, nitrogen dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal clusters on unimolecular film.
Substrate unimolecular film used in the present invention is the unimolecular film of a kind of amphiphilic polymer or straight chain fatty acid or aliphatic amide (carbonatoms n=12～22) etc., preferably a kind of amphiphilic polymer, its hydrophilic head can be carboxyl, amino, sulfydryl isopolarity group, preferably carboxyl.Amphiphilic polymer is poly-di-acetylenic acid, and chain length is a 10-30 carbon atom, and three key positions are 10, the 12-position, and 6,8-position or 2, the 4-position wherein has 10,12-diine neocerotic acid, 2,4-diine tricosanic acid, straight chain fatty acid has C
19H
39COOH (20 acid) etc.
The used metal of the present invention can be transition element and precious metal, that is: gold, and silver, copper, cobalt, if nickel and six kinds of platinum family elements etc. are preparation atoms metal dot matrix, preferably gold.The used reductive agent of the present invention can be a hydrazine, hydrazonium sulfate, boron prussiate etc.; Constant pressure is π=15-30mN/m; Ultraviolet wavelength is 240nm-260nm; Metal-salt or metal salt complex are water-soluble, easily dissociated.
Unimolecular film for polymkeric substance, can spread film after the first polymerization, also can make unimolecular film polymerization on the throne on liquid level of polymer monomer obtain the unimolecular film of polymkeric substance, the introducing of metal can will (contain) metal ion solution and add end liquid before sprawling unimolecular film, also can add end liquid after the unimolecular film polymerization is finished.
Preparation flow can be used three-pit system, also can use single channel process.For the former, at first need in three grooves of " three slot types " membrane instrument (this laboratory self-control) [S.X.Ji, C.Y.Fan, F.Y.Ma, X.C.Chen, L.Jiang, Thin.Solid Films, 242,16 (1994)], add finite concentration (10 respectively
-6～10
-4M) (contain) aqueous solution (or pure water, treat to add metal ion again after the unimolecular film polymerization), pure water and the finite concentration (10 of metal ion
-7～10
-4M) the reductive agent aqueous solution, sprawl unimolecular film at first groove, and successively adsorb and polymerization (or first polymerization, absorption again), (15-20mN/m) is pushed into this polymeric film in second cell body that is full of pure water under constant surface pressure then, make the abundant desorption of those loose bonded ions, be pushed into (containing) metal ion reduction that the 3rd cell body will adsorb at last again; For the latter, slightly different is, must adsorb (containing) metal ion in the polymkeric substance unimolecular film after, it is transferred to slide glass with level or vertical crystal pulling method, in pure water, fully after the rinsing, place the reductive agent aqueous solution to finish reduction of metal ion again.The metal atomic cluster that the present invention obtained is below 10 nanometers, and the sequential 2 D dot-matrix of atoms metal or cluster is the flat square lattice.
Biggest advantage of the present invention is that lattice is very stable, can stablize under the room temperature to reach more than 48 hours, has greatly exceeded the lattice steady time that present prior art for preparing goes out; Secondly, because the present invention is based on the LB film, thereby for the less metal of some surface tension, as metallic gold, can realize atomic ordered dot matrix truly, rather than the monoatomic layer roughly on the statistical significance.The 3rd, the parameter of lattice is constant, helps to study very much the two-dirnentional structure of metal.In addition, consider the specific effect of some metal and biomolecules, the metal lattice of this sequential 2 D is expected to help to realize the parsing of the submicroscopic(al) structure of some biomacromolecule.
Accompanying drawing 1: the gold atom two-dimensional points system of battle formations of using (STM) observational technique to obtain.
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment 1: the two-dimentional structure of single channel process system gold atom
In standard unimolecular film groove, be end liquid with the pure water, will be dissolved in 10 in the chloroform, 12-diine neocerotic acid unimolecular film spreads in the groove, then unimolecular film is depressed into constant pressure π=18mN/m, and balance is after 20 minutes, with the polymerization of 254nm UV-irradiation.Subsequently, in end liquid, inject certain amount of H AuCl
4The aqueous solution makes the AuCl in the end liquid
4 -Concentration is 5 * 10
-5M; After 2 hours, polymeric film is transferred to (individual layer) on the hydrophobic slide glass, slide glass is immersed fully rinsing in the pure water, and then immerse 10 with horizontal crystal pulling method
-5In the hydrazonium sulfate aqueous solution of M, reductase 12 0 minute.At last slide glass is cleaned, nitrogen dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal atoms.
Embodiment 2: the two-dimentional structure of three-flute legal system gold atom
In three grooves of " three slot types " membrane instrument, be docile and obedient preface respectively and add 5 * 10
-5M HAuCl
4The aqueous solution, pure water and 5 * 10
-6The hydrazonium sulfate aqueous solution of M, to be dissolved in 10 in the chloroform, after 12-diine neocerotic acid unimolecular film spreads over first groove, with the polymerization of 250nm UV-irradiation, (20mN/m) carefully is pushed into this polymeric film in second cell body that is full of pure water under constant surface pressure then, left standstill ten minutes, and be pushed into the AuCl of the 3rd cell body at last again absorption
4 -The ion reduction, translational speed was as the criterion by the pure water cell body with 20 minutes, and the recovery time gets and was advisable in 20 minutes.At last, with vertical crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal atoms.
Embodiment 3: three-pit system prepares monodispersed pt atom bunch
In three grooves of " three slot types " membrane instrument, be docile and obedient preface respectively and add 10
-5M H
2PtCl
6The aqueous solution, pure water and 10
-6The hydrazonium sulfate aqueous solution and 10 of M
-5M H
2PtCl
6The aqueous solution, in the chloroform poly-(2 will be dissolved in, 4-diine tricosanic acid) after unimolecular film spreads over first groove, with the polymerization of 260nm UV-irradiation, under constant surface pressure (30mN/m), this polymeric film is pushed in second cell body that is full of pure water, left standstill ten minutes, be pushed into the PtCl of the 3rd cell body at last again absorption
6 -The ion reduction, translational speed and recovery time are with embodiment 2.At last, with horizontal crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal atoms.
Embodiment 4: single channel process prepares monodispersed silver atom cluster
In standard unimolecular film groove, with 5 * 10
-5M AgNO
3The aqueous solution is end liquid, with the eicosanoic acid (C that is dissolved in the chloroform
19H
39COOH) sprawling unimolecular film spreads in the groove, then unimolecular film is depressed into constant pressure π=20mN/m, balance 30 minutes is transferred to (individual layer) on the hydrophobic slide glass with vertical crystal pulling method with the eicosanoic acid unimolecular film, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-5The hydrazonium sulfate aqueous solution and 5 * 10 of M
-5M AgNO
3In the aqueous solution, reductase 12 0 minute.At last slide glass is cleaned, nitrogen dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal clusters.
Embodiment 5: the two-dimentional structure of single channel process system gold atom
In standard unimolecular film groove, be end liquid with the pure water, will be dissolved in 10 in the chloroform, 12-diine neocerotic acid unimolecular film spreads in the groove, then unimolecular film is depressed into constant pressure π=18mN/m, and balance is after 20 minutes, with the polymerization of 260nm UV-irradiation.Subsequently, in end liquid, inject certain amount of H AuCl
4The aqueous solution makes the AuCl in the end liquid
4 -Concentration is 5 * 10
-5M; After 2 hours, polymeric film is transferred to (individual layer) on the hydrophobic slide glass, slide glass is immersed fully rinsing in the pure water, and then immerse 10 with horizontal crystal pulling method
-5In the boron potassium cyanide aqueous solution of M, reductase 12 0 minute.At last slide glass is cleaned, nitrogen dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal atoms.
Embodiment 6: three-pit system prepares monodispersed pt atom bunch
In three grooves of " three slot types " membrane instrument, be docile and obedient preface respectively and add 10
-6M H
2PtCl
6The aqueous solution, pure water and 10
-6The hydrazonium sulfate aqueous solution and 10 of M
-5M H
2PtCl
6The aqueous solution, in the chloroform poly-(2 will be dissolved in, 4-diine tricosanic acid) after unimolecular film spreads over first groove, with the polymerization of 240nm UV-irradiation, under constant surface pressure (30mN/m), this polymeric film is pushed in second cell body that is full of pure water, left standstill ten minutes, be pushed into the PtCl of the 3rd cell body at last again absorption
6 -The ion reduction, translational speed and recovery time are with embodiment 2.At last, with horizontal crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal clusters.
Embodiment 7: single channel process prepares monodispersed silver atom cluster
In standard unimolecular film groove, with 5 * 10
-5M AgNO
3The aqueous solution is end liquid, with the eicosanoic acid (C that is dissolved in the chloroform
19H
39COOH) sprawling unimolecular film spreads in the groove, then unimolecular film is depressed into constant pressure π=20mN/m, balance 30 minutes is transferred to (individual layer) on the hydrophobic slide glass with vertical crystal pulling method with the eicosanoic acid unimolecular film, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-7The hydrazonium sulfate aqueous solution and 5 * 10 of M
-5M AgNO
3In the aqueous solution, reductase 12 0 minute.At last slide glass is cleaned, nitrogen dries up.On unimolecular film, form sequential 2 D dot-matrix less than 10 nano metal clusters.
Claims (13)
1. method that forms on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms is characterized in that:
The two-dimentional structure of single channel process system atoms metal:
In standard unimolecular film groove, with the pure water is end liquid, spread in the groove being dissolved in the amphiphilic polymer in the chloroform or the unimolecular film of straight chain fatty acid or aliphatic amide, then unimolecular film is depressed into constant pressure, after the balance, amphiphilic polymer need be used the UV-irradiation polymerization, or directly spreads the good film of polymerization, injects 5 * 10 then in end liquid
-6M to 5 * 10
-4The aqueous solution of M metal-salt or metal salt complex, the concentration that makes the metal ion in the end liquid is 5 * 10
-6M to 5 * 10
-4M; With horizontal crystal pulling method or vertical crystal pulling method polymeric film is transferred on the hydrophobic slide glass, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-6M to 10
-4Reduce in the reductive agent aqueous solution of M, at last slide glass is cleaned, nitrogen dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal atoms on unimolecular film.
2. method that forms on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms is characterized in that:
The two-dimentional structure of three-flute legal system atoms metal:
In three grooves of " three slot types " membrane instrument, in first groove, add 5 * 10
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex add pure water in second groove, add 5 * 10 in the three-flute
-7M to 5 * 10
-4The reductive agent aqueous solution of M, after the unimolecular film that is dissolved in amphiphilic polymer in the chloroform or straight chain fatty acid or aliphatic amide spread over first groove, amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, under constant surface pressure, this polymeric film carefully is pushed into then in second cell body that is full of pure water, after leaving standstill, the last metal ion reduction that is pushed into the 3rd cell body with absorption again, after the reduction, with horizontal crystal pulling method or vertical crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal atoms on unimolecular film.
3. method that forms on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms is characterized in that:
Three-pit system prepares the two-dimentional structure of monodispersed metal atomic cluster:
In three grooves of " three slot types " membrane instrument, in first groove, add 5 * 10
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex add pure water in second groove, add 5 * 10 in the three-flute
-7M to 5 * 10
-4The reductive agent aqueous solution and 5 * 10 of M
-6M to 5 * 10
-4The metal-salt of M or the aqueous solution of metal salt complex, after the unimolecular film that is dissolved in amphiphilic polymer in the chloroform or straight chain fatty acid or aliphatic amide spread over first groove, amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, under constant surface pressure, this polymeric film is pushed in second cell body that is full of pure water, after leaving standstill, be pushed into of the metal ion reduction of the 3rd cell body again with absorption, after the reduction, with horizontal crystal pulling method or vertical crystal pulling method unimolecular film is transferred on the slide glass, nitrogen gas stream dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal clusters on unimolecular film.
4. method that forms on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms is characterized in that:
Single channel process prepares the two-dimentional structure of monodispersed metal atomic cluster:
In standard unimolecular film groove, with 5 * 10
-6M to 5 * 10
-4The aqueous solution of M metal-salt or metal salt complex is end liquid, spread in the groove being dissolved in the amphiphilic polymer in the chloroform or the unimolecular film of straight chain fatty acid or aliphatic amide, amphiphilic polymer need carry out the UV-irradiation polymerization, or directly spread the good film of polymerization, then unimolecular film is depressed into constant pressure, after the balance, unimolecular film is transferred on the hydrophobic slide glass with horizontal crystal pulling method or vertical crystal pulling method, slide glass is immersed fully rinsing in the pure water, and then immerse 10
-7M to 10
-4The reductive agent aqueous solution and 5 * 10 of M
-6M to 5 * 10
-4In the aqueous solution of M metal-salt or metal salt complex, after the reduction, at last slide glass is cleaned, nitrogen dries up, and forms the sequential 2 D dot-matrix less than 10 nano metal clusters on unimolecular film;
5. as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms, it is characterized in that described constant pressure is π=15-30mN/m, described ultraviolet wavelength is 240nm-260nm.
6. as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms, it is characterized in that the hydrophilic head of described amphiphilic polymer is carboxyl, amino or sulfydryl polar group.
7. the method that on unimolecular film, forms less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms as claimed in claim 6, it is characterized in that described amphiphilic polymer is poly-di-acetylenic acid, chain length is a 10-30 carbon atom, three key positions are 10, the 12-position, 6,8-position or 2,4-position.
8. the method that forms on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms as claimed in claim 7 is characterized in that described poly-di-acetylenic acid is 10,12-diine neocerotic acid or 2,4-diine tricosanic acid.
9. as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms, it is characterized in that the carbonatoms n=12-22 of described aliphatic amide.
10. as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms, it is characterized in that described straight chain fatty acid is C
19H
39COOH.
11., it is characterized in that described metal is transition element, gold and silver, copper, cobalt, nickel or six kinds of platinum family elements as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms.
12., it is characterized in that described reductive agent is hydrazine, hydrazonium sulfate or boron prussiate as claim 1,2,3 or 4 any described methods that on unimolecular film, form less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms.
13. as claim 1,2,3 or 4 any described methods that form on unimolecular film less than 10 nano metal clusters or sequential 2 D dot-matrix of metallic atoms, the sequential 2 D dot-matrix that it is characterized in that described atoms metal or cluster is the flat square lattice.
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| CN1075842C true CN1075842C (en) | 2001-12-05 |
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| CN100506687C (en) * | 2005-06-20 | 2009-07-01 | 中国科学院化学研究所 | Method for forming two dimensional ordered lattice of metal or metal alloy quantum dots on solid interface, in which dot diameters are less than or equal to 5nm |
| CN109396415B (en) * | 2017-08-17 | 2019-11-22 | 清华大学 | Gold nano cluster and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168676A (en) * | 1994-10-13 | 1997-12-24 | 爱德华B·戈德伯格 | Materials for the production of nanometer structures and use thereof |
| CN1180102A (en) * | 1997-10-10 | 1998-04-29 | 中国科学院感光化学研究所 | Oxidase function compound sensitive film containing hydrophobic nanometre prill and its making method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168676A (en) * | 1994-10-13 | 1997-12-24 | 爱德华B·戈德伯格 | Materials for the production of nanometer structures and use thereof |
| CN1180102A (en) * | 1997-10-10 | 1998-04-29 | 中国科学院感光化学研究所 | Oxidase function compound sensitive film containing hydrophobic nanometre prill and its making method and use |
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