CN101573781A - Digital alloys and methods for forming the same - Google Patents

Abstract

Alloys of tunable compositions and corresponding optical, electrical and mechanical properties are described. Also described are their uses in optoelectronic devices and material interfaces.

Description

Digital alloy and manufacture method thereof

Background of invention

Technical field

The application relate to alloy with controlled composition and physical property (comprising photoelectricity and engineering properties), they in electrooptical device purposes and make the method for this type of alloy.

Description of Related Art

Electrooptical device comprises that electricity arrives electric transducer, for example light diode (comprising solar cell), photistor, photo resistance, laser, Light-Emitting Diode (LED), optical fiber or the like to light or light widely.No matter which kind of type, the operation of electrooptical device is at least a based on two kinds of basic processes, promptly produces electron-hole pair by photonic absorption, or by reorganization electronics and hole and ballistic phonon.

Semi-conducting material has unique electronics band structure, and this structure can be impacted by the quantum mechanical effects of light.Therefore, they are to make the selected material of electrooptical device.In semi-conducting material, the highest occupied frequency hand generally is full of fully, is called valence band; And minimum not occupied frequency hand is called the conduction band.Electronics in valence band can absorb photon energy, and is excited to the conduction band, thereby stays the hole in valence band.When having the electronics of quantity as can be known in the conduction band, semi-conducting material promptly become have conductive.On the contrary, the electronics in the conduction band can with the hole recombination in the valence band, thereby cause the emission that photon is spontaneous or be stimulated.

The photoelectric property of semi-conducting material depends on the capacity volume variance (" band gap ") between its valence band and the conduction band to a great extent.For example in the process that produces electron-hole pair, band gap is that electronics is energized into directly measuring of the required minimum photon energy in conduction band from valence band.When electronics and hole recombination, the photon energy of band gap decision emission.Correspondingly, the control band gap is the effective way of control photoelectric property and electrooptical device output variable.

Band gap is the inwardness of given semi-conducting material.Band gap can be by mixing impurity adjustment according to known method in semi-conducting material.Selectively, produce the semiconducting alloy that forms by two or more semiconductor group branches.The band gap of this type of alloy is different with the semiconductor component, it typically is the function of band gap and component relative quantity.

Generally speaking, in the process that produces new alloy, allow two or more elements to form a lattice.More generally, two types bianry alloy (for example AIAs, InP, GaAs or the like) forms ternary or quaternary alloy.Therefore, the lattice match of component is important for the strain and the defective that reduce to obtain alloy.

Fig. 1 shows semi-conductive band-gap energy of each III-V of family (eV) and lattice constant.Two binary semiconductor alloy A IAs almost have identical lattice constant (about 5.65) with GaAs in the diagram.Their band gap is respectively 2.20eV and 1.42eV.Since lattice constant match, so AIAs and GaAs are suitable for forming metastable ternary alloy three-partalloy, this alloy Al _xGa _1-xAs represents (atomic percentage that x is AIAs in the alloy).The band gap of this ternary alloy three-partalloy is the function of x, also is the function of the band gap of pure AIAs and GaAs.This example shows that the composition by the control semiconducting alloy changes the approach of band gap.

The composition of control alloy is estimated to produce the new material with adjustable photoelectricity or engineering properties.At present, make semiconducting alloy (Al for example by growth technology (for example organometallic chemical vapor precipitation (MOCVD) or molecular beam epitaxy (MBE)) _xGa _1-xAs, ln _xGa _1-xN and Al _xGa _1-xN).Yet,, generate these epitaxial loayers and still have technical challenge although the material of relative strain tolerance and defective tolerance is arranged.Especially be difficult to keep their mechanical stability and integrality owing to strain, limit the thickness of formed lamella conversely.Form the influence that control also is subjected to strain in the material.

Some semi-conducting materials do not have acceptable lattice match, and this lattice match allows them to form stable compound or heterostructure with standard mass crystallization or growth technology.Therefore, handle special band gap or have particular alloy and form to be unusual difficulty, and to use current semiconductor technology sometimes be impossible.

Brief overview

The present invention describes semiconductor or the metal alloy based on simple substance and/or the formation of bielement nano structural constituent (or " nano-component ") template.Generally speaking, provide or handle template and make it comprise a plurality of dissimilar binding sites, and the distance between its site is a nanoscale with controlled ratio.Select first kind binding site, it has special affinity for first kind nanostructure component, and selects the second class binding site, and it has special affinity for the second type nanostructure component.The nanostructure component of first and second types is incorporated into template with controlled manner.

Thereby can make the first and second type groups of nanostructures divide the new material of formation simulation multielement alloy by rigging.Can select size and their position and ratios on template of nanostructure component, nano-component, so that the collection of discrete nano-component simulation multielement alloy.

The method of the device of alloying and this type of alloy of use has also been described in addition.

More specifically, the composition that embodiment provides comprises: a plurality of templates, each template comprises at least one first binding site and at least one second binding site, first binding site has the affinity of specificity combination to first nano particle of first material, second binding site has the affinity of specificity combination to second nano particle of second material, and wherein selected template comprises first binding site of x percentage and second binding site of y percentage; A plurality of first nano particles are incorporated into first binding site separately; A plurality of second nano particles are incorporated into second binding site separately; Wherein thereby rigging makes first material and second material form alloy with the stoichiometric ratio of x: y.

Another embodiment provides the method that forms alloy, this method comprises: form at least one biological template, this template has at least one first binding site and at least one second binding site, first binding site has the affinity of specificity combination to first nano particle of first material, and second binding site has the affinity of specificity combination to second nano particle of second material; Control template makes the quantity of first binding site and second binding site than being x: y (0＜x＜1,0＜y＜1); First nano particle is combined with separately first binding site; Second nano particle is combined with separately second binding site; Comprise the alloy of first material and second material with formation.

Another embodiment provides the electrooptical device that comprises alloy, and this alloy forms certainly: form a plurality of biological templates, each template has more than first binding site and more than second binding site, and template has first binding site and second binding site of selected ratio; Make more than first binding site coupling on a plurality of first nano particle components and the biological template, first component is made up of at least two kinds of different elements; Make more than second binding site coupling on a plurality of second nano particle components and the template, second component is made up of at least two kinds of different elements, and at least a element of second component is different from least a element of first component; Select the quantitative proportion of first binding site and second binding site, thereby make template more than first nano particle and more than second nano particle assembling can be formed alloy.

Another embodiment provides the electrooptical device that comprises above-mentioned alloy, and also being removed after alloy forms with a plurality of biological templates is prerequisite.

Another embodiment provides solar battery structure, and it comprises: semiconductor substrate; With the photosensitive layer of semiconductor substrate coupling, this photosensitive layer comprises alloy, and wherein alloy comprises: a plurality of templates, each template have more than first binding site and more than second binding site, and template has first binding site and second binding site of selected ratio; Make more than first binding site coupling on a plurality of first nano particle components and the biological template, first component is made up of at least two kinds of different elements; Make more than second binding site coupling on a plurality of second nano particle components and the template, second component is made up of at least two kinds of different elements, at least a element of second component is different from least a element of first component, select the number ratio of first binding site and second binding site, so that template can be assembled into alloy with more than first nano particle and more than second nano particle.

Another embodiment provides lithium ion battery, it comprises: anode, comprise cobalt, oxygen and be selected from gold, copper substantially and the low resistive metal of silver, the ratio of low resistive metal and cobalt is controlled at selectively less than 4, thereby and be placed on the cell resistance of minimizing battery in the anode; Negative electrode; And be placed on the electrolytic liquid of transfer lithium ions between anode and the negative electrode, wherein cobalt and low resistive metal form in the presence of a plurality of templates, each template has a plurality of first binding site and a plurality of second binding sites that low resistive metal had affinity that cobalt had affinity, the quantity of the binding site of low resistive metal is less than the quantity of the binding site of cobalt basically, and has first and second binding sites of selected ratio.

Another embodiment provides structure, and it comprises: first conducting shell; Second conducting shell; And be positioned over intersheathes between first and second conducting shells, intersheathes is formed by the biological template that at least one contains at least one first binding site and at least one second binding site, first binding site has the affinity of specificity combination to first nano particle of first material, second binding site has the affinity of specificity combination to second nano particle of second material, thereby control template makes first binding site and the quantity ratio of second binding site be x: y (0＜x＜1,0＜y＜1), first nano particle is combined with separately first binding site; Second nano particle is combined with separately second binding site; Comprise the alloy of first material and second material with formation.

The accompanying drawing summary

In the drawings, identical similar element or the effect of reference number representative.Not chi drafting in proportion of the size of element and relative position in the accompanying drawing.For example the shape of various elements and angle not to scale (NTS) chi are drawn, and in these elements some can enlarge arbitrarily, and the position of placing makes drawing more clear.In addition, the given shape of the element of drafting is not any information that is intended to pass on about the element-specific true form, and only selects for figure is discerned easily.

Fig. 1 is band-gap energy and the lattice constant curve chart of knowing.

Fig. 2 A and Fig. 2 B show according to the digital alloy (digital alloy) of an embodiment and the gained band gap is graphic.

Fig. 3 shows the through engineering approaches band gap according to an embodiment.

Fig. 4 A and Fig. 4 B represent template and the binding site according to different embodiments.

Fig. 5 A and Fig. 5 B represent graphic according to the different chaperoninses (chaperonin) of various embodiments.

Fig. 6 shows the orderly 2D array according to the template of an embodiment.

Fig. 7 represents only to realize with binary composition the template of ternary compound band gap.

Fig. 8 represents to have according to an embodiment template of through engineering approaches binding site of the special nano particle of selected ratio.

Fig. 9 represents the nano particle with each binding site coupling of the template of Fig. 8.

Figure 10 represents to simulate first ratio of the binary composition binding site of selected ternary compound.

Figure 11 represents to simulate the different proportion in the identical combination site of different ternary compounds.

Figure 12 A and Figure 12 B represent multilayer solar battery, the ternary compound that this multilayer simulation is made according to the principle that shows among Figure 10 and Figure 11.

Figure 13 represents various band gap graphic of material in the solar cell.

Figure 14 represents graphic according to the various nano-pillar on the template of the present invention.

Figure 15 is illustrated in nano-pillar graphic of the Figure 14 that uses in the electrooptical device.

Figure 16 represents to have the template of element binding site of the simulation chemical compound specifically bind of selected ratio.

Figure 17 represents the template of same element, and it has the binding site of the different compounds of simulation of different proportion.

Figure 18 represents the principle of Figure 16 and Figure 17 explanation according to the present invention, the lithium ion battery that has gold element in the male or female selected location.

Figure 19 is the LED schematic diagram of making according to an embodiment.

Figure 20 represents graphic according to the intermetallic structure of an embodiment.

Detailed Description Of The Invention

The alloy of the composition with accurate control has been described.These alloys also refer to " digital alloy " herein, and it is the heterocomplex of two or more type nanostructure components (for example " nanocrystal "), and these components are assembled in the presence of template.As what describe in further detail, the nanostructure component is nano level construction unit (building block), and it can be simple substance material (comprising individual element) or binary material (comprising two elements).Template is biological or abiotic support, and it comprises the binding site of specificity in conjunction with selected nanocrystal, and wherein the binding site distance of separating is nanoscale or a few ten nanometers level.The composition of digital alloy is by the nanocrystal sets branch decision of chemical dose, and this chemical dose is controlled by the distribution of binding site.

Because small-sized (the having only several atoms usually) of nanocrystal, and their (several to dozens of nanometers usually) closer to each other, electronics can not distinguish a nanocrystal component and another nanocrystal sets branch as the material that separates.As an alternative, the behavior of the two or more different materials in the duplet nanocrystal is average, thinks that they are single alloys.Therefore can produce new material by handling the nanoscale component with adjustable macroscopic property.

Fig. 2 A shows the graphic of digital alloy 10 that the thin layer by the binary nanocrystal of two types constitutes, and wherein 20% is first binary nanocrystal 14 (for example InN) and 80% be second nanocrystal 18 (for example GaN).Fig. 2 B represents how discriminating digit alloy 10 of electronics 30.From the angle of electronics, make the conduction band 34 of GaN and the 38 average conduction bands 42, conduction band of InN to obtain digital alloy, it is by In _0.2Ga _0.8The N representative.Similarly, the valence band 50 of the valence band 46 of GaN and InN on average obtains corresponding In _0.2Ga _0.8The valence band 54 of N alloy.Therefore, the band-gap energy value of digital alloy is between pure InN and GaN band-gap energy.In other words, electronic recognition alloy 10 is by the new (ln that forms _0.2Ga _0.8N) ternary alloy three-partalloy, rather than the binary composition InN of two separation and GaN.As will be described in detail below, the stoichiometry of each element is controlled by using template in new composition, and this stencil design is in conjunction with two binary composition (for example InN and GaN ratio are 20%: 80% among Fig. 2 A) with selected ratio.The band gap of this ternary alloy three-partalloy is the stoichiometric function of single component.

Macroscopic view, the new block materials of nanocrystal component simulation of assembling, this integral material has the average properties of component material.Therefore, these digital alloys have light, electricity and engineering properties widely, are difficult to reach in its normally naturally occurring material.For example two-layer InGaN (InGaN), one of them band gap are 1.7eV, and another is 1.1eV, can reach two-layer face (multi-junction) battery 50% the maximal efficiency in theory that connects more.Epitaxial growth with InGaN of high percentage In is difficult to finish at present under the condition that does not have material inhomogeneity and low optical efficient.Current, be difficult to make up material usually, yet method as described herein if the bielement nano structure is obtainable, can easily make up this type of layer with any selected band gap so with particular design and selected band gap.

Therefore, the alloy that particular relates to comprises: a plurality of templates, each template comprises at least one first binding site and at least one second binding site, first binding site has the affinity of specificity combination to first nano particle of first material, second binding site has the affinity of specificity combination to second nano particle of second material, selects template with first binding site that comprises x percentage and second binding site of y percentage; A plurality of first nanocrystals are in first binding site separately; A plurality of second nanocrystals are in second binding site separately; Wherein rigging makes first material and second material form alloy, and the stoichiometric proportion of first material and second material is x: y in this alloy.

Fig. 3 represents the through engineering approaches according to the required band gap of the digital alloy of forming control.Term used herein " digital alloy " refers to the combination of any materials, and described material comprises semiconductor, metal, metal oxide and insulator.As shown in Figure 3, first material (for example GaN) has conduction band 20 and valence band 21.Between conduction band 20 and the valence band 21 is band gap apart from d1.For insulator, band gap is usually above 3eV, and can not overcome by the electronics in the valence band, and for metallic conductor, then do not have band gap, and valence band and conduction band are overlapping.As mentioned above, in semiconductor, band gap is small enough to make the electronics in the valence band can overcome band gap under given conditions, is excited to the conduction band.Fig. 3 has also explained the band gap of second material (for example InN), and it has conduction band 22 and valence band 23, therefore has by the band gap apart from the d2 representative between two bands.Make template, its have with user's design and selected ratio (x: first binding site y) and second binding site, x and y are the percentage of first and second binding sites, x+y equals 1.Select first and second binding sites to be incorporated into first and second materials respectively.Therefore, the ratio of first material and second material is stoichiometric proportion x: y on the template.The digital alloy of gained is by two components (ln for example _xGa _yN or ln _xGa _1-xN) preparation, but therefore and will have valence band 25, conduction band 24 and identify and stoichiometric through engineering approaches band gap d based on two components.

X used herein and y can be represented (0＜x＜1,0＜y＜1) by proper fraction or percentage.For example, in two component alloys (being x+y=1),, be interpreted as that so x also can represent to do proper fraction 0.2 if first binding site exists with first binding site and second binding site of the combination of x=20%.And the selected ratio of first binding site and the second class binding site can use x: y to represent, this ratio is corresponding to the stoichiometric proportion of two kinds of materials that constitute the gained alloy.

Fig. 4 A represents to comprise the template 50 of support 54, and this support comprises first binding site 58 and second binding site 62 of selected ratio 20%: 80%.First binding site 58 and the 66 specificity couplings of first nanocrystal, second binding site 62 and the 70 specificity couplings of second nanocrystal.Therefore, if first nanocrystal is that the InN and second nanocrystal are GaN, the gained alloy that is formed by template 50 assemblings can be by ln so _0.2Ga _0.8N represents.

Fig. 4 B represents another template that contains support 84 80, and this support comprises first binding site 58 and second binding site 62 of selected ratio 40%: 60%.As what below will go through, can use as the binding site of the same-type explained among Fig. 4 A and same relevant nanometer crystal.Yet the selected ratio of first binding site and second binding site is adjusted into 40%: 60%.Therefore, if first nanocrystal is that the InN and second nanocrystal are GaN, the gained alloy that is formed by template 80 assemblings can be by ln so _0.4Ga _0.6N represents.

Therefore, can use suitable template with the synthetic alloy of controlled manner, especially by selecting ratio corresponding to the binding site of different nanocrystal components.The alloy that obtains is made of the nanoscale structures unit of two or more different materials, and it is not subjected to the restriction of lattice match or geometry.Can be averaged in on those of nanocrystal component with the congenital relevant physical property (for example light, electricity, magnetic and engineering properties) of the given composition of alloy.Explained after a while as this paper, depended on required final use, can the based semiconductor nanocrystal and metal nanocrystal prepare semiconducting alloy and metal alloy respectively.

A. Template

" template " can be arbitrarily synthetic and natural material, and it provides the binding site that nanocrystal can coupling.As described herein, thus select template to realize the precision control of binding site in significant mode on the statistics, promptly control their composition, amount and position.Can use based on biology and abiotic template.

Have affinity because proved peptide sequence, therefore preferably incorporate the biological template of peptide sequence into as binding site to many variety classes nanocrystal specificitys and selective binding.And, thereby biological template can through engineering approaches comprise predetermined binding site in predetermined spatial relationship (for example separating several to dozens of nanometers).They especially have the advantage of control figure alloy composition.Biological template comprises for example biomolecule and the biological support of fusogenic peptide sequence.

As below will be in greater detail, can operate biological template by genetic engineering, thereby the may command position on template produces specific binding site.Abiotic template also can be operated by the accurate model of binding site with nanometer resolution.

1. Biological template:

As mentioned above, can be based on science of heredity through engineering approaches biological template (for example protein and biological support) thus the type of control binding site (for example peptide sequence), their positions on template and they separately density and/or with the ratio of other binding sites.For example see people such as Mao, C.B., (2004) Science, 303,213-217; Belcher, people such as A., (2002) Science 296,892-895; Belcher, people such as A., (2000) Nature 405 (6787) 665-668; People such as Reiss, (2004) Nanoletters, 4 (6), 1127-1132, Flynn, people such as C., (2003) J.Mater.Sci., 13,2414-2421; Mao, people such as C.B., (2003) PNAS, 100 (12), 6946-6951, these documents its integral body by reference incorporate this paper into.This helps the composition of control binding site on biological template and the ability of distribution.

In specific embodiments, biological template comprises first peptide sequence of x percentage and second peptide sequence of y percentage.Because first peptide sequence has specificity affinity and second peptide sequence to first nanocrystal of first material second nanocrystal of second material is had the specificity affinity, therefore can form the alloy of first material and second material.More particularly, alloy comprises selected stoichiometry (x: first material y) and second material, this stoichiometry is by the decision of the relative quantity of first binding site and second binding site.

In other embodiments, first binding site and second binding site must all not be present on the template of single type.Alternatively, first binding site can separately exist on the template of the first kind, and second binding site is positioned on the template of second type.The relative percentage of first binding site and second binding site (x: y) can control by the selected ratio of the first kind template in the alloy composition and the second type template.

A. Biomolecule

In specific embodiments, biological template is a biomolecule, for example protein." biomolecule " refers to biogenetic any organic molecule.Usually, biomolecule comprises a plurality of subunits (construction unit) that are connected into sequence by chemical bond-linking.Each subunit comprises at least two reactive groups, and for example hydroxyl, carboxyl and amino are in order to form interconnective key between subunit.The example of subunit includes but not limited to: amino acid (natural and synthetic) and nucleotides.The example of biomolecule comprises peptide, protein (comprising cell factor, growth factor or the like), nucleic acid and polynucleotides." peptide sequence " refers to the two or more amino acid with the connection of peptide (acid amides) key.Amino acid structure unit (subunit) comprises the amino acid (for example beta-amino acids and homoamino acid (homoamino acids)) that naturally occurring a-amino acid and/or non-natural exist.And alpha-non-natural amino acid can be the chemical modification form of natural amino acid." protein " refers to natural or the big molecule of through engineering approaches, and it has with the peptide sequence is the primary structure of feature.Except that primary structure, protein also presents secondary and the tertiary structure that determines their final geometries.

Can in heredity, orientation carry out because protein is synthetic, so they can easily operate and functionalization, comprise required peptide sequence (being binding site) thereby make on the desired location in the prlmary structure of protein.Then, protein can be assembled so that template to be provided.

Therefore, in various embodiments, template is the biomolecule that comprises at least one first peptide sequence and at least one second peptide sequence.In one embodiment, template is the protein that the nanocrystal of at least two kinds of metamaterials is had binding affinity that has of native protein or through engineering approaches.

In specific embodiments, biological template is a chaperonins, its through engineering approaches and have binding affinity to the particular type nano particle, and it can be self-assembled into fibrillation or orderly 2-d array (for example seeing U.S. Patent application No. 2005/0158762).Chaperonins is to be self-assembled into many difformities protein of (comprising duplex structure) easily, and forms crystal array at the surface of solids.Usually, need atriphos (ATP) and Mg ²⁺Mediate crystal and form, for example see U.S. Patent application No. 2005/0158762.Shown the example that how forms digital alloy among Fig. 5 A, Fig. 5 B and Fig. 6 from chaperonins.

Fig. 5 A and Fig. 5 B show the diagram of the ring-type chaperonins 100 with 9 subunit 10s 4.Placed perforate 108 at the chaperonins center.Perforate is characterised in that it is the functional structure territory, and it comprises and can have peptide sequence to the specificity affinity of the nanocrystal of metamaterials by genetic engineering operation.In addition, the functional structure territory has the geometry of good definition, can determine with its size as the nanocrystal of nuclear.

By genetic engineering, binding site (do not have show) may reside on the subunit of each or arbitrary number.As an example, Fig. 5 A shows that 4 subunits have first binding site of coupling in first kind nanocrystal 112, and 5 subunits have second binding site of coupling in the second class nanocrystal 116.

The subunit of chaperonins also can through engineering approaches and have first binding site and at outside second binding site that exists of chaperonins in perforate.Shown in Fig. 5 B, chaperonins 102 is incorporated into 9 first nanocrystals 112 in the perforate 108 and is incorporated into 9 second type nanocrystals 114 on outside 124.

The subcellular structure that natural chaperonins is made up of 14,16 or 18 identical subunits that are called heat shock protein.These 60kDa subunits are arranged in 16-18nm height, the wide stacked rings of 15-17nm.Many kinds of chaperoninses are checked order, and the structural information that can obtain them instructs genetic manipulation.The sudden change chaperonins that one or more amino acid has been changed by site directed mutation can be developed net shape and the binding ability that is used to operate chaperonins.For example see people such as McMillan A., (2002) Nature Materials, 1,247-252.The chaperonins variant that is to be understood that genetic engineering or chemical modification also is the suitable template that this paper defines.

In another embodiment, template is a S-layer protein, and it can be self-assembled into orderly two-dimensional array, also can the combining nano crystal.(for example see people such as Dietmar P., Nanotechnology (2000) 11,100-107).Natural S-layer protein forms the outermost layer cell membrane component of broad spectrum of bacteria and archeobacteria.They are made up of single albumen or glycoprotein (Mw40-200kDa), and the scope of its unit cell dimension is 3-30nm.It is thick that the S-layer is generally 5-10nm, and the hole of identical size (for example 2-8nm) is arranged.Proved S-layer protein in surface of solids crystallization again, the S-layer self assembly product that perhaps is positioned over this carrier can be used to induce the formation of CdS particle or gold nano grain, for example sees people such as Shenton, Nature (1997) 389,585-587; With Dieluweit et al.Supramolec Sci, (1998) 5,15-19.The genetic engineering or the chemical modification variant that are to be understood that S-layer protein also are suitable templates as herein described.

In another embodiment, biological template is an apoferritin.Apoferritin is the ferritin that lacks hydrated ferric oxide (ferrihydrite).In life entity, native ferritin participates in iron metabolism.It is made up of 24 subunits, produces the hollow-core construction in the hole with the general 8nm of diameter and the about 2nm of wall thickness.The hole stores 4500 iron (III) atom with the form of paramagnetic hydrated ferric oxide usually.In apoferritin, removed this hydrated ferric oxide, and other nano particle can be merged in the hole that is produced.Subunit in the ferritin closely is bundled together; Yet, have passage to the hole.Some passages comprise suitable binding site, described site bond, for example cadmium, zinc and calcium.The ferritin molecule can be induced under these bivalent ions situations and be assembled into orderly arrangement existing.About using ferritin to come the detailed description of combining nano crystal in U.S. Patent number for example the 6th, 815, No. 063 and the 6th, 713, No. 173, to find as template.The genetic engineering or the chemical modification variant that are to be understood that apoferritin also are suitable template as herein described.

In another embodiment, template is an e. coli dna polymerase III β subunit, and this albumen is homodimer protein.Its general structure takes to have the loop configuration of the wall of the hole of about 3.5nm and thick about 3.4nm.The inner surface of wall comprises 12 short α spirals, and 6 β lamellas form outer surface.Inner surface can be introduced amino acid or peptide sequence by through engineering approaches, and it can be caught the nanocrystal of various materials or become its nuclear.The genetic engineering or the chemical modification variant that are to be understood that e. coli dna polymerase also are suitable templates as herein described.

B. biological support

In other embodiments, template is the biological support that merges one or more peptide sequences." biological support " refers to comprise the polymolecular biological structure of the complexity of a plurality of binding sites.In preferred embodiments, genetically engineered biological support is blended in quantity, distribution and the spacing of the binding site (for example peptide sequence) of biological support with control.

The example of biological support includes but not limited to virion, bacteriophage, amyloid fiber and capsid.These biological supports (natural and mutant form with it) can form ordered structure on being placed into the multiple surface of solids time.For example see people such as Flynn, C.E., " Viruses as Vehicles forGrowth, Organization Assembly of Materials (as the virus of material growth, tissue assembling media), " Acta Materialia (2003) 51,5867-5880; Scheibel, people such as T., PNAS (2003), 100,4527-4532; Hartgerink, people such as J.D., PNAS (2002) 99,5133-5138; McMillan, people such as A.R., Nature materials (2002), 247-252; Douglas, people such as T., Advanced Materials (1999) 11,679-681; And Douglas, people such as T., Adv.Mater. (2002) 14,415-418; With people such as Nam, " GeneticallyDriven Assembly of Nanorings Based on the M3 Virus (assembling that drives based on the heredity of the nano-rings of M3 virus), " Nanoletters, a-e.

In a particular, thereby the M13 bacteriophage can have the one or more particular peptide sequences that are blended on the capsid protein through through engineering approaches.For example, verified can in capsid protein, introduce to gold or silver-colored nanocrystal have in conjunction with and/or the peptide sequence (for example seeing Application No. the 11/254th, No. 540) of nucleation affinity.

In another embodiment, amyloid fiber can be used as biological support, thereon nano particle can in conjunction with and be assembled into orderly nanostructure." amyloid fiber " refers to that diameter is the proteinaceous fiber of about 1-25nm.Under given conditions, one or more common soluble protein (being precursor protein matter) can fold and be assembled into fibre structure, and become soluble.No matter the structure of precursor protein matter source, amyloid fiber is made up of the β chain of assembling usually.Precursor protein matter used herein can comprise natural or non-natural amino acid.Amino acid can further have the aliphatic acid tail to modify.The suitable precursor protein matter that can transform or be assembled into amyloid fiber comprises for example RADA 16 (Ac-R+AD-AR+AD-AR+AD-AR+AD-A-Am) (joining gold) (SEQ ID NO:1), biotin-R (+) GD (-) SKGGGAAAK-NH ₂(joining gold) (SEQ ID NO:2), WSWR (+) SPTPHVVTD (-) KGGGAAAK-NH ₂(in conjunction with silver) (SEQ ID NO:3), AVSGSSPD (-) SK (+) KGGGAAAK-NH ₂(joining gold) (SEQ ID NO:4) or the like.For example see people such as Stupp, S.I., PNAS 99 (8) 5133-5138,2002 and people such as Zhang S., PNAS 102 (24) 8414-8419,2005.

Similar with protein template, but thereby biological support also is preferably the peptide sequence that makes of through engineering approaches can optionally express with special ratios and distribute.

C. the assembling of biological template and gathering

The formation of alloy depends on the assembling or the gathering of template, makes the nanocrystal that is incorporated into each template close.In specific embodiments, template can be assembled before the combining nano crystal.In other embodiments, template can be before assembling the combining nano crystal.

The natural tendency that biological template (for example biomolecule and biological support) has in solution or assembles on matrix.Some biological templates can spontaneously be self-assembled into the 2D or the 3D structure of height lenticular.

Fig. 6 shows the diagram of assembling the orderly 2D array 130 of the template that forms by two class chaperoninses 134 and chaperonins 138.First kind chaperonins 134 can be in conjunction with first nanocrystal 142 in its perforate 146.The second class chaperonins 138 can be in conjunction with second nanocrystal 150 in its perforate 154.In this embodiment, 2D array 130 comprises 30% first kind chaperonins 134 and 70% the second class chaperonins 138, and it is corresponding to 30% first nanocrystal 142 and 70% second nanocrystal 150.As what indicated, the relative component of first and second nanocrystals in the gained alloy is determined by the ratio of their template corresponding.

It should be noted that, thereby at random, polycrystalline or the impalpable structure of formation also can be placed or assemble to template, as long as selected template comprises first and second binding sites of required ratio, and though they be present on the same type template or be present in the corresponding first kind and second class template on.

2. Abiotic template

Template also can be inorganic template, for example silicon, germanium, quartz, sapphire (sapphire) or other acceptable materials.This template can with proper ratio required component is had the binding site coupling of specificity affinity.For example binding site (for example protein, for example streptavidin (streptavidin) or avidin (avidin)) can be fixed on the selected location, and with the selected fixed ratio to inorganic template (for example silicon).Nanocrystal or other nano particles can be directly and the binding site coupling.Selectively, nanocrystal at first can with binding partners (for example biotin of the streptavidin) coupling of binding site, thereby be fixed on the silicon matrix by the strong affinity of (for example biotin and streptavidin) between the binding partners.

Be to be understood that other binding sites (self-assembled monolayer that for example comprises functional groups) can be used for fixing, and as the template that functional groups is had the nanocrystal of special affinity.

Importantly, binding site (for example streptavidin) moulding on inorganic template, its each other in several nanometers in tens nanometers, thereby guarantee suitable spacing also to be arranged in conjunction with thereon nanocrystal.Can realize the fixing and moulding of protein on matrix by any known method of this area.For example, streptavidin can pass through nano-imprint lithography art (nanoimprint lithography) with nanometer resolution moulding on silicon oxide substrate, for example sees people such as Hoff, J.D., and Nano Letters (4) 853, and 2004.

B. Binding site

As mentioned above, the template of digital alloy forms finally and is controlled by person's character, spacing and the relative scale of at least two class binding sites on the template.Minimal structure element in " binding site " or " binding sequence " finger print plate, its relate to or participate in template in conjunction with vigor.Preferably, binding site can be controlled with the composition of the nanocrystal of its coupling, size and mutually.

Term used herein " combination " and " coupling " and they name word form separately is used interchangeably, and attracted to formation stable compound on the binding site thereby be often referred to nanocrystal.The potentiality that attracts is also referred to as " affinity " or " binding affinity " at this paper, it can be any stable phase mutual effect between two entities, comprises absorption and adhesion.Usually, interaction is natural non-covalent; Yet, also may be covalent bond.

Usually, binding site comprises the functional groups of biomolecule, for example sulfydryl (SH), hydroxyl (OH), amino (NH ₂) and carboxylic acid (COOH).The sulfydryl of cysteine joining gold particle (Au) effectively for example.More generally, binding site is the subunit sequence of biomolecule, and not only a functional groups is responsible for affinity.In addition, the conformation of sequence, secondary structure and local CHARGE DISTRIBUTION also can be made contributions to the potentiality of affinity.

" specificity combination " and " selective binding " are the technical terms that the technical staff is readily appreciated that, when referring to the binding ability of biological template, it refers to determine that a kind of nanocrystal of material is present in the association reaction of the heterogeneous population of other materials nanocrystal, and other materials can not be with significant mode combination on the statistics under the same conditions.Can determine specificity by using the suitable positive and negative control and optimization routine condition.

The composition of peptide sequence is fixed on the template, thereby produces the selected composition of nanoparticle structure unit, and various different peptide sequence can be on template with at random or orderly mode arrange.For the composition of template mixture, each designs according to the peptide sequence that at least one has the selective affinity of material of a nanoparticle structure unit, thereby selects this composition to produce the given composition of nanoparticle structure unit.Template self can be placed or self assembly at random or with orderly fashion.

Can use the evolution screening technique to select certain material is had the peptide sequence of specific bond affinity or selectivity identification certain material.The detailed description of this technology can find in U.S.'s publication application No. 2003/0068900, No. 2003/0073104, No. 2003/0113714, No. 2003/0148380 and No. 2004/0127640, and all these is the name with the application's assignee Cambrios Technologies Corporation.These lists of references, comprise described sequence table all by reference its integral body incorporate this paper into.

In brief, this technology is utilized phage display, yeast displaying, cell surface display or other, can express multiple proteins or peptide sequence.The situation of phage display for example, bacteriophage (for example M13 bacteriophage) storehouse can produce by insert many different peptide sequences in the bacteriophage population.Especially, thus the genetic sequence that can operate bacteriophage provides many copies of particular peptide sequence on the bacteriophage.The pVIII protein of for example about 3000 copies can vertically be arranged on the M13 phage particle with the form of oldered array.PVIII protein can be modified to and comprise the particular peptide sequence, and this peptide sequence can be used as the nuclear that the specific target nanocrystal forms.The protein that will have high affinity to different specific target nanocrystals is exposed to more and more stricter environment, up to selecting the protein that high affinity is arranged.Separate this protein then and identify its peptide sequence.

This technology is very strong because its allow quick discriminating can specificity in conjunction with the peptide sequence of the nanocrystal of any given material.And, as following will be discussed in detail, in case identified a peptide sequence, promptly can with controlled manner it be incorporated in the biological template by genetic engineering.

Binding site can with suitable nanocrystal by directly combining or " affinity " coupling.In the case, the preformed nanocrystal of predetermined composition and size can be hatched with template, and between suitable binding site and nanocrystal association reaction takes place.

Also may template can cause that nanocrystal is from solution nucleation on the template in opposite directions.Thereby nucleation is to exist under the condition of template by changing the process that the precursor original position forms nanocrystal.Usually, the nanocrystals of original position generation is in template and continued growth.As mentioned above, the functional structure territory of particular organisms template (for example protein, for example chaperonins and apoferritin) with controlled composition and geometry.Therefore, the functional structure territory provides binding site and physical constraint, thereby makes the nanocrystal of nuclear can grow into controlled dimensions (by the geometry decision in functional structure territory).The detailed description that forms nano particle by nucleation process can be at for example Flynn, people such as C.E., (2003) J.Mater.Sci., 13,2414-2421; Lee, people such as S-W, (2002) Science 296,892-895; Mao, people such as C.B., (2003) PNAS, 100, (12) are found in No. the 2005/0164515th, 6946-6951 and the U.S.'s publication application.

Table 1 show identified many semiconductors and metal material are had the example of the peptide sequence of special affinity.Peptide sequence and the interactional mechanism of given material have also been shown.

Table 1

¹Flynn, C.E. wait the people, " Synthesis and organization of nanoscale II-VIsemiconductor materials using evolved peptide specificity and viralcapsid assembly (utilizing the synthetic and establishment of the nanoscale II-VI semi-conducting material of variant peptides specificity and viral capsid assembling); " (2003) J.Mater.Sci., 13,2414-2421.

²Lee, people such as S-W, " Ordering of Quantum Dots Using GeneticallyEngineered Viruses (using the quantum dot ordering of genetically engineered virus), " (2002) Science296,892-895.

³Mao, people such as C.B., " Viral Assembly of Oriented Quantum DotNanowires (the virus assembling wiry of directed quantum dot nano), " (2003) PNAS, vo1.100, no.12,6946-6951.

⁴US2005/0164515

⁶Mao, C.B. wait the people, " Virus-Based Toolkit for the Directed Synthesis ofMagnetic and Semiconducting Nanowires (being used for the directed synthetic kit based on virus of magnetic semiconductor nano metal silk); " (2004) Science, 303,213-217.

⁷Reiss, people such as B.D., " Biological route to metal alloy ferromagneticnanostructures (biological approach of the ferromagnetic nanostructure of metal alloy) " (2004) NanoLetters 4 (6), 1127-1132.

⁸Huang, Y. wait the people, " Programmable assembly of nanoarchitectures usinggenetically engineered viruses (using the programmable assembling of the nanometer construct of genetically engineered virus) " (2005) Nano Letters 5 (7), 1429-1434.

⁹No. the 11/254th, 540, U.S. Patent application

¹¹Lee, S-W. wait the people, " Cobalt ion mediated self-assembly of geneticallyengineered bacteriophage for biomimic Co-Pt hybrid material (being used for the self assembly of cobalt ions mediation of the genetic engineering bacteriophage of biosimulation Co-Pt heterozygote material) " Biomacromolecules (2006) 7 (1), 14-17.

¹²Whaley, S.R. wait the people, " Selection of peptides with semiconductorbinding specificity for directed nanocrystal assembly (assembling has semiconductor in conjunction with specific peptide to the directional nano crystal in selection) " (2000) Nature, 405 (6787), 665-668.

¹³US2003/0148380

¹⁴US2006/0003387

¹⁵Peelle, people such as B.R., " Design criteria for engineering inorganicmaterial-specific peptides (design standard of through engineering approaches inorganic material specific peptide) " (2005) Langmuir 21 (15), 6929-6933.

¹⁶No. the 60/620th, 386, U.S. Provisional Patent Application

C. Nanocrystal

" nanocrystal ", " quantum dot " or " nano particle " are often referred to the nanoscale structures unit of digital alloy.Nanocrystal be many atoms gathering or bunch, inorganic material normally.Nanocrystal used herein normally diameter less than 10nm.More generally, the diameter of nanocrystal is less than 5nm or less than 1nm.They can be crystalline, polycrystalline or unbodied.

As mentioned above, the nanocrystals of at least two different compositions (material) is in the template or the formation alloy composition that flocks together.In specific embodiments, nanocrystal can be the simple substance material, comprises metal and semiconductor.In other embodiments, nanocrystal can be a binary material, and it is the stable compound or the alloy of two elements.

Therefore, the composition of nanocrystal can be by formula A _mB _nRepresent that wherein A and B are single elements.Letter m and n represent A and B atomic percentage separately in the nanocrystal, are defined as 0≤m≤1; 0≤n≤1; M+n=1; Prerequisite is that m and n can not be 0 simultaneously.When n was 0, nanocrystal was the simple substance materials A.When m or n were not 0, nanocrystal was binary compound A _mB _n

Simultaneously, nanocrystal different or second material can be used formula C _pD _qExpression, wherein C and D are single elements, and the value of p and q is 0≤p≤1; 0≤q≤1; P+q=1; Prerequisite is that p and q can not be 0 simultaneously.

M used herein and n (or p and q) are atomic percentages (atom %) separately, corresponding to the stoichiometric proportion of A in the binary compound and B.They also can be the forms of proper fraction.For example there is the binary compound of 50%A and 50%B can use A _0.5B _0.5Expression.Be defined as proper fraction or atomic percentage although should be appreciated that m and n, they all require 0≤m≤1 and 0≤n≤1, binary compound A _mB _nAlso can be with the formulate that comprises integer.Those skilled in the art is easy to discern the different expression formulas that these formula only are same composition.A for example _0.5B _0.5Can be expressed as AB, A ₂B ₂Or A ₅B ₅, perhaps be expressed as Any Digit, as long as the stoichiometric proportion of A and B (m: n) keep identical.Therefore, will be understood that these expression formulas are A _mB _nEqual composition.

1. Simple substance material (n=0)

Suitable metallic element comprises Ag, Au, Sn, Zn, Ru, Pt, Pd, Cu, Co, Ni, Fe, Cr, W, Mo, Ba, Sr, Ti, Bi, Ta, Zr, Mn, Pb, La, Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca Nb, Tl, Hg, Rh, Sc, Y.Suitable semiconductor element comprises Si and Ge.

In specific embodiments, thus the nanocrystal of simple substance material can form bianry alloys with different simple substance material alloysization.In other embodiments, thus the nanocrystal of simple substance material can form ternary alloy three-partalloy with the binary compound alloying.

2. Binary material (m ≠ 0 and n ≠ 0)

Binary material is the stable compound of two elements.In specific embodiments, binary material or binary compound are metals, comprise two kinds of metallic elements, for example Cu and Ni, Sn and In or the like.

In other embodiments, binary material is a semiconducting compound.Usually, when A was IIIA family element (for example Al, Ga, In or T1), B was VA family element (for example N, PAs or Sb).When A was IIB family element (for example Zn, Cd or Hg), B was VIA family element (O, S or Se).Known many stable binary semiconductors of forming that has include but not limited to AIAs, AIP, AIN, GaAs, GaP, GaN, InAs, ZnSe, CdS, InP and InN or the like.

In specific embodiments, the first binary material (A _mB _n) and the second binary material C _pD _qThereby in conjunction with forming quaternary alloy, wherein all 4 kinds of elements A, B, C and D are different elements on template.In other embodiments, B is identical element with D, and second binary material can be expressed as C _pB _qTherefore the gained composition is the ternary alloy three-partalloy that comprises A, B and C.

Metal and semi-conductive nanocrystal are commercially available, Quantumsphere for example, Inc. (Santa Ana, CA), Invitrogen (Carlsbad, CA) and Nanoprobes (Yaphank, NY).They also can prepare by means known in the art, for example pass through thermal decomposition of sol-gel technique, Organometallic precursor or the like.These preformed nanocrystals do not rely on template and prepare, and can pass through specificity affinity and the suitable binding site coupling of template.For example preformed nano-scale particle can directly be incorporated into binding site, normally is the peptide sequence of specific nano particle screening and evaluation.Selectively, nano particle can carry out finishing with required binding reagents (for example biotin), and this binding reagents can be by strong and the specific affinity and binding site (for example streptavidin) coupling of biotin and streptavidin.

In other embodiments, nanocrystal can from solution mutually nucleation.The nucleation thing forms the process of nanocrystal by transformation precursor original position under the situation that template exists.Usually the nano particle of original position generation is in conjunction with growing on the functional structure territory of template and at least a portion therein.Precursor normally finally forms the soluble-salt of the element of nanocrystal.For example, the nanocrystal of CdS can be from containing Cd ²⁺And S ^2-Solution in nucleation.The more detailed description that forms nano particle by nucleation process can be at for example Flynn, C.E. wait the people, " Synthesis andOrganization of Nanoscale II-VI Semiconductor Materials Using EvolvedPeptide Specificity and Viral Capsid Assembly (utilizing the synthetic and establishment of the nanoscale II-VI semi-conducting material of variant peptides specificity and viral capsid assembling) ", (2003) J.Mater.Sci, 13,2414-2421; Lee, people such as S-W, " Ordering of Quantum DotsUsing Genetically Engineered Viruses (using the quantum dot ordering of genetically engineered virus) ", (2002) Science 296,892-895; Mao, people such as C.B., " Viral Assembly ofOriented Quantum Dot Nanowires (the virus assembling wiry of directed quantum dot nano) ", and (2003) PNAS, vol.100, no.12 finds among 6946-6951 and the US2005/0164515.

D. Alloy

As mentioned above, (x: y), first nanocrystal of first material and second nanocrystal of second material can be formed alloy by regulation and control to the relative quantity by first binding site on the control template and second binding site.Specifically, when first material be by A _mB _nThe compound and second material of expression are by C _pD _qThe expression compound the time, the gained alloy can be used (A _mB _n) _x(C _pD _q) _yExpression, wherein

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n can not be 0 simultaneously, p and q can not be 0 simultaneously.

In specific embodiments, A, B, C and D differ from one another, and the gained alloy is a quaternary alloy.

In other embodiments, A, B and C differ from one another, and B is identical with D, and the gained alloy is a ternary alloy three-partalloy.

In other other embodiments, n=q=0, gained alloy are bianry alloy A _xC _y, or A _xC _1-x(because x+y=1).

Can realize the alloy of multiple composition by the relative quantity of selecting corresponding binding site on suitable nanocrystal component and the control template.

For example, under the situation of specificity in conjunction with the template of the binding site of GaN of the specificity that x percentage is provided when existence in conjunction with the binding site of InN and y percentage, thereby can select InN and GaN to form alloy (lnN) as the nanocrystal component _x(GaN) _yOr ln _xGa _yN _X+yBecause x+y=1, the gained alloy also can be used ln _xGa _1-xN represents.Therefore, by controlling the amount of binding site separately, the alloy that can obtain to have multiple band gap.The formation of these alloys is not subjected to the restriction of lattice match.More specifically, because alloy is by nanoscale structures unit (nanostructure component) formation of molecular level, so do not consider common strain and the defective that is associated with epitaxial growth.

Other alloys of corresponding useful band gap comprise for example GaAs _xP _1-x(forming), Ga by GaP and GaAs _xLn _1-xP (forming), Al by GaP and InP _xLn _1-xP (forming) and Al by AIP and InP _xGa _1-xAs _yP _1-y(forming) by AIP and GaAs.

E. Make the method for digital alloy

Other embodiments are described the method for alloying, comprising:

Select biological template, it has second binding site (0＜x＜1 of first binding site and the y percentage of x percentage, 0＜y＜1), first binding site has the specific binding affinity of first nano particle to first material, and second binding site has the specific binding affinity of second nano particle to second material;

First nano particle combines with separately first binding site,

Second nano particle combines with separately second binding site; With

Formation contains first material of stoichiometric proportion x: y and the alloy of second material.

In specific embodiments, first material is by A _mB _nThe compound of expression, second material is by C _pD _qThe compound of expression, the gained alloy can be used (A _mB _n) _x(C _pD _q) _yExpression, wherein

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n can not be 0 simultaneously, and p and q can not be 0 simultaneously.

In other embodiments, select biological template to comprise and make the biological template through engineering approaches by genetic manipulation.Especially, reach first binding site (for example first peptide sequence) and second binding site (for example second peptide sequence), thereby realize control biological template by biological template through engineering approaches preposition, spacing and scale on template.

In preferred embodiments, biological template is a protein.Protein as an example includes but not limited to the variant of variant, apoferritin or its genetic engineering or chemical modification of variant, S-layer protein or its genetic engineering or chemical modification of chaperonins or its genetic engineering or chemical modification or the variant of e. coli dna polymerase III β subunit or its genetic engineering or chemical modification.

In other embodiments, biological template is the biological support that merges with first peptide sequence and second peptide sequence.As mentioned above, biological support can be for example virion, bacteriophage, amyloid fiber or capsid.

Fig. 7 shows the method for making digital alloy, and from template 151, this template is had required binding site ratio by through engineering approaches, thereby forms simulation ternary compound Al _xGa _1-xThe material of As.Template 151 has more than first binding site 152, and this binding site has affinity to nanocrystal 156 (being AIAs in this example).This template also comprises more than second binding site 154, and this binding site has affinity to nanocrystal 158 (being GaAs in this example).Thereby the ratio of selecting first binding site 152 and second binding site 154 realizes the gained alloy of required composition.For example, thus M13 virus can genetically modified specific site in virus capsid protein matter has the binding site (for example peptide sequence) of these or other selected nanocrystal.Then, template 151 is exposed to the liquid of a plurality of nano particles that comprise binary compound AIAs.

The AIAs nano particle can optionally be attached to self on the binding site 152 of template 151 separately, and non-cohesive or append on the binding site 154.Template 151 also is exposed to the liquid that contains the GaAs nano particle, and the GaAs nano particle will self be attached on the binding site 154.In some embodiments, required liquid is the liquid solution of separating, and template sequentially is exposed to these liquid, and in other embodiments, template can be exposed to simultaneously and have both single liquid solution of binary composition.

Fig. 8 and Fig. 9 represent to form according to an embodiment each step of ternary compound material.In the step that Fig. 8 shows, according to before in Fig. 7, showed with explain the same, any acceptable matrix is provided, for example template 168.Have a plurality of binding sites 164 and binding site 167 on the template 168, required nanocrystal component is had separately affinity.The nanocrystal component that forms digital alloy can have required arbitrarily element and form.In the example that Fig. 8-Figure 11 provides, they are that binary is formed, for example InN and GaN.From the angle of electronics, thereby need binding site enough closely to form continuous material.The spacing of adjacent binding site is usually at several nanometers and a few ten nanometers level.Thereby the ratio of selecting binding site 164 and binding site 167 provides the requisite number of the component of binary composition 160 and binary composition 162.Correspondingly, thereby template 168 contains different binding sites through through engineering approaches, and these binding sites can optionally be attached to nanocrystal separately.In addition, for continuous material is provided, binding site is to each other apart from number nanometer (for example being less than 10nm).

Provide a plurality of nanocrystals 160 and nanocrystal 162 average marks to be dispersed in wherein solution.Nanocrystal can be the form of nano particle, nano-pillar or other can accept form arbitrarily.In one embodiment, provide the single solution that has two types of nanocrystals.Selectively, can provide the solution of two kinds of separation, its each have the nanocrystal of average dispersion.In containing the solution of crystal, place a plurality of templates 168.Solution at room temperature mixes, and contains suitable pH balance, thereby makes template 168 that activity be arranged when using techniques well known.Can place on matrix or a plurality of templates 159 of self assembly, thereby alloy-layer is provided, its controllable groups becomes corresponding required physical property.

If nanocrystal is in the solution of two kinds of separation, template 168 is positioned in first solution, and mix, suitable nano particle in the binding site additional solutions of specific nanocrystal, then template 168 is shifted out first solution, and be positioned in second solution that contains second nanocrystal 160, continue to mix.

When this template is exposed to the solution that has by nano particle that binding site separately is made up of the material of affinity or quantum dot; this material will be incorporated into template so; it can form the oldered array of material, thereby makes 168 simulations of final template have separately the three kinds of different elements of ratio rather than the ternary alloy three-partalloy of two kinds of different binary compounds.The use of nanocrystal, quantum dot and nano particle allows the template of these type of nanometer materials to form, thereby with physics, chemistry and electronics purpose simulation ternary alloy three-partalloy.

Can make up template 168 and make many different-alloys of forming by difference.For example thereby pVIII protein can be with particular peptide sequence through engineering approaches as template.The peptide sequence that the selectivity affinity is provided and is connected in various semiconductor nanocrystals (for example ZnS or CdS) is known, perhaps can and identify by the known method screening.For example known A7 and the growth that can discern and control ZnS of Z8 peptide on pVIII protein, and J140 provides the selectivity identification of CdS.See " Viral assembly of oriented quantum dot nanowires " (virus assembling of directed quantum dot nano silk) PNAS of people such as Mao, on June 10th, 2003, Vol.100, people's such as No.12 and Flynn " Synthesis and organization of nanoscale II-Vlsemiconductor materials using evolved peptide specificity and viralcapsid assembly " (utilizing the synthetic and establishment of the nanoscale II-VI semi-conducting material of variant peptides specificity and viral capsid assembling) J.Mater.Chem., 2003, Vol.13, pages2414-2421, each all incorporates this paper by reference into.

Use other template of different peptide combinations can be used to produce matrix, thereby this matrix is used to form composition simulation ternary or the quaternary compound that has In, Ga, Al, As, N, P and various other elements in the binary composition.

A kind of strength of this technology is to use identical binary composition, thereby produces the different ternary compounds with different band gap with identical nano particle, and is indicated as Figure 10 and Figure 11.Show that in Figure 10 template 161 has the first selected ratio of binding site 167 and binding site 164.Show that in example per two binding sites 164 have 8 binding sites 167.When template 161 was exposed to the liquid solution of the nano particle with a plurality of InN160 and GaN162, nano particle separately was incorporated into the binding site that it is had the specificity affinity, thereby produced final ln _0.2Ga _0.8The composition of N.

Figure 11 represents different templates 163, and wherein identical binding site 164 and binding site 167 are had different proportion relative to each other by through engineering approaches.In this example, binding site 164 is 3: 7 or 30%: 70% with the ratio of binding site 167.Correspondingly, when template 163 is exposed to identically when having the liquid solution of bielement nano particle, the nanocrystal of different proportion is attached on the template.Wherein, nano particle is InN and GaN, and have ln with formation final the composition _0.3Ga _0.7The character of N.Can form the nano-component of any required ratio under the template existence condition, it controls final alloy composition, for example ln conversely _0.35Ga _0.65N or the like.

F. Use

Alloy composite described herein is corresponding to the inaccessiable useful light of conventional method, electricity and engineering properties by multi-component alloys or compound.The genetically engineered strong technology of given biological template drives, can be by obtaining the alloy that the height customizable is formed corresponding to the different binding sites of nanocrystal component separately on the control template.

Therefore, various embodiments all relate to the device that uses alloy composite as herein described.

1. Photoelectric cell or solar cell

Solar radiation provides the photon scope to be about the utilisable energy of 0.4-4eV.Electrooptical device (for example photoelectric cell) can be collected the specific photon energy of this scope and convert thereof into electric energy.Usually, electrooptical device is based on the semi-conducting material of the direct band gap with the given photon energy of coupling.After absorbing photon energy, the electronics in valence band is excited to the conduction band, and electronics can free migration there.Equally, in valence band, produce the hole.The migration of these charge carriers (for example electronics and hole) forms electric current.

The band gap of present obtainable semi-conducting material is only corresponding to the very narrow part of extensive solar radiation.Have the light that is lower than semiconductor band gap energy and be not absorbed or convert to electric energy.The light that is higher than band-gap energy can be absorbed, and still the electron-hole pair that produces is recombinated rapidly, and loses the energy that is higher than band gap with the form of heat.For example, have the direct band gap of about 1.1eV based on the photoelectric cell of crystalline silicon, it is all lower than most photon energies.Therefore, be up to about 25% efficient based on the solar cell of silicon.

Therefore, there is the inherent efficiency restriction that semi-conducting material is forced in existing photoelectric cell.At present, do not find that a kind of semi-conducting material can mate solar radiation widely fully.

Seek higher efficient with the semiconductor stack of different band gap, make solar cell have one or more faces that connect.In more than ten years in the past, developed forming from two semiconductor Ga _0.5Ln _0.5P/GaAs and three semiconductor Ga _0.5Ln _0.5P/GaAs/Ge piles up.These advantages that connect the face battery are Ga more _0.5Ln _0.5The lattice match of P, GaAs and Ge is relative better.Usually in having the face that the connects battery of different components layer, lattice match is crucial for producing low defective or defect free crystal more.Crystal defect has negative effect to semi-conductive optical characteristics, because defective is caught charge carrier and limited obtainable electric current and voltage.Correspondingly, connect the face battery more and normally be subjected to the restriction that can the low-cost suitable semiconductor material of integrating generally lacks.

Recognize ternary alloy three-partalloy (In recently _xGa _1-xN) can see U.S.'s publication application No. 2004/0118451 as the basis of complete spectrum solar cell, but at the good ln that controls of development _xGa _1-xAlso there are many technological challenges in the N epitaxial loayer process.

Semiconducting alloy as herein described is formed by control under the condition that exists in template provides adjustable band gap, and does not consider the coupling of lattice and polarity.May produce the alloy composite of band gap with corresponding complete scope solar radiation.

Figure 12 A and Figure 12 B represent the solar cell 174 that principle according to the present invention is formed with the digital alloy array.Solar cell 174 is made of the semi-conducting material with 3 layers of customization digit groups compound as described herein.Solar cell 174 has electrode 182 in its side regions.In one embodiment, the low-resistance electric layer that constitutes by semiconductor or some other contact materials of high doped and the coupler electrode of its apex zone.Also known use GaAs matrix is finished the circuit that produces electricity from solar cell as base material thereby conducting electrode adheres in this area on it, even and do not show among the figure that this structure also belongs to the scope of application of the present invention.Known GaAs layer can produce electricity when being exposed to the DT self, and its efficient can reach the efficient of 20%-25% in the 16%-25% scope.This efficient can use structure disclosed herein to improve basically.

Shown in Figure 12 A, the formation of solar cell is made up of the digital alloy that a plurality of usefulness method disclosed herein makes up, as indicated among prior figures 7-Figure 11.The layer 176, layer 178 and the layer 180 that make the digital alloy template layer that makes up based on the principle of Fig. 7-Figure 11 or big array form three separation.Select the ratio of the nano-component in the layer 176, thereby simulation has ln _X3Ga _Y3The ternary compound of N character.This material will have required band gap and electrical property when being exposed to the DT, thereby produce from the daylight that is different from the frequencies that layer 178 and layer 180 produce.Correspondingly, layer 176 can obtain the bigger solar cell of gross efficiency 174 thus from being different from the extracting section energy of layer 178 and layer 180 light frequency of extracting.

Equally, layer 178 and layer 180 form single structure in vicinity and at layer 176 top.These layers also are made up of a plurality of binary nanocrystal of identical binary compound InN and GaN, but the ratio difference.Compound ratio separately is different, thereby simulation has the quaternary compound of photoelectric property, extracts energy with the different piece from spectrum of sunlight.Because use identical binary material, thereby the lattice structure of crystal is may be mutually compatible in some structures, and forms contiguous layer 178 and layers 180 in same crystal structure and physics each other contacts.Semi-conductive 3,4 or 5 layers provide very efficient solar cell, and the element ratio of each layer is slightly different.

Shown in Figure 12 A-Figure 12 B, solar cell 174 certainly is made up of multiple different digital alloy material widely, and it is with the combination in any of disclosed nanocrystal of the application or nano particle.For example, arbitrary digital alloy can comprise the compound that contains other element (for example P, Al, Cd, cadmium selenide, cadmium telluride and other materials) in layer 176, layer 178 and the layer 180.An advantage of the present invention is that different component does not need to have similar lattice constant, and can not be alloy under reference condition or do not have the chemical combination each other.For example, according to principle disclosed herein, use binding site located adjacent one another on the template, GaP can be formed at identical digital alloy with InSb or InAs.Because these materials have very different lattice constants, so be very difficult or impossible with their moulding on the same matrix of conventional batteries.Yet, the template formation of nanocrystal allows to have different lattice constants and materials with different properties is combined to form digital alloy, wherein nanocrystal is incorporated into template with selected ratio, in conjunction with based on to the affinity of binding site rather than based on lattice match or miscellaneous stipulations parameter.Correspondingly, in one embodiment, the digital alloy of the solar cell of Figure 12 A can comprise that lattice constant is that mutual distance is greater than .3

To .5

Mutual distance is greater than 1 under (seeing Fig. 1 chart) or the certain situation

Material, and be provided in the identical layer of digital alloy in using the semi-conducting material that forms according to template of the present invention.

Figure 12 B represents to make up according to the difference of the solar cell of another embodiment.In this made up, electrode 182 was in the top and the bottom of battery 174, electrode 184 layer 186, layer 187 and layer 188 separately between.In the solar cell of Figure 12 B, top layer 186 can be the binary material of standard, and GaN for example is two or more layers 187 and the layer 188 that has with the superiors' 186 different bandgap properties below it.Operating among Figure 13 of each layer shows among Figure 12 A and Figure 12 B.

As shown in figure 13, the solar cell with 174 diagram representatives has daylight to collide on it.Daylight has the multiple frequency across extensive spectrum.Top material 180 has the first band gap E _G1, and with first efficient generation based on the daylight adjustable frequency.Second material 178 has specific gap tunable E _G2, extract energy with spectrum from the frequency that is different from material 180.Therefore, this band gap E _G2Produce extra electricity effectively, greatly improve the overall efficiency of solar cell 174.The one or more layers by 176 representatives subsequently have different band gap, and are littler than the band gap of layer 180 and layer 178 in this embodiment, and produce electricity based on the different piece of spectrum, further improve the overall efficiency of solar cell 174.Can produce to the electricity of the load 190 shown in Figure 12 B, and can on the solar cell of the supplemantary electrode shown in Figure 12 A 182, place similar circuit, in order simply not show this load.

Figure 14 represents the nanocrystal of a plurality of nano-pillar forms, and it can use according to principle disclosed herein.Matrix 192 can be used as the template of the technology that this paper explained of use.Form nanocrystal from each nano-pillar, each nano-pillar has different photoelectric properties.More than first nano-pillar 194 has first band gap.More than second nano-pillar 196 has second band gap, and more than the 3rd nano-pillar 198 has the 3rd band gap.The specific bond site of each provides on template 192 in these nanocrystals.Therefore template 192 has a large amount of nano-pillar located adjacent one another with different photoelectric properties on single template.Show a purposes of this based composition in Figure 15, wherein template 192 is immersed in the conductive of material, thereby as the electrode of solar cell.Also can provide apex electrode 191.Daylight collides to produce on composition 151 and separates from variant nano-pillar 194, nano-pillar 196 and nano-pillar 198.Thereby these nano-pillar have different band gap through through engineering approaches separately usually, and therefore the different piece from spectrum of sunlight produces.

Correspondingly, can form the material of individual layer, thereby very efficient solar cell is provided.This material layer can be can not put letter thin, because nano-pillar is in the scope of nanocrystal.In some embodiments, the nanocrystal width that forms nano-pillar 194, nano-pillar 196 and nano-pillar 198 is in the 6-10 nanometer range, and length is in the 500-800 nanometer range.This size is corresponding to the size based on the template of biological virus, described virus for example this paper discuss and in citing document disclosed M13 or bacteriophage.Correspondingly, can provide the solar cell 199 of gross thickness less than 1000 nanometers, it can utilize, and all obtainable frequencies produce from daylight in the spectrum of sunlight.Further improve efficient if desired, can provide so and be parallel to those the nanocrystal of addition type shown in Figure 14 and Figure 15, this nanocrystal is with the form of nano-pillar with different band gap, each is organized nano-pillar and absorbs daylight from the different frequency of spectrum, and based on absorbed and produce.Another advantage of the structure of Figure 14 and Figure 15 is the collision on an equal basis on each nano-pillar of all daylight, must be by each layer before arriving the bottom.Correspondingly, with the structure of Figure 14 and Figure 15 even can more efficient generation.

2. Lithium ion battery

Another purposes according to digital alloy of the present invention is in lithium ion battery, as Figure 16-shown in Figure 180.Lithium battery has anode and negative electrode, and negative electrode generally includes the carbon of various graphite forms, wherein inserts lithium atom, and anode generally includes Co, Mn, O or some other metal oxide.Advantageously make lithium ion battery in the long basically life-span, have lower resistance and higher production capacity.One of difficulty is that the material of current use has limited conductivity, and helps being unfavorable for low-resistance current delivery as the character of the male or female in the lithium ion battery.

According to embodiment disclosed herein, the digital alloy that forms can have the high conductance metal, it appends to the negative electrode of lithium ion battery, or selectively appends to anode or the two poles of the earth, thereby the conductivity, the electric current that increase lithium ion battery up hill and dale produce and useful life.

Gold (Au) is the high conductance metal.If provide too many Au atom or the nanocrystal of Au at negative electrode or anode, the operation meeting of lithium ion battery is destroyed so.With at present known construct and alloy technology is the several atoms that are difficult to just add metal (for example Au), and makes it that suitable spacing be arranged and be in proper proportion, thereby strengthens conductibility and do not hinder battery to produce the ability of electricity.For example, known generation AuCo molecule.Yet if all Co combine with corresponding Au atom in the battery, the operation of lithium ion battery is destroyed basically so.

According to the principle of this paper instruction, the selected ratio of Au and Co can be provided, it goes up basically that the conductibility that increases battery and electric current produce ability and the operation characteristic of not destroying lithium battery.Figure 16 represents to have the template 202 of the binding site of the Au nanocrystal of selected ratio and Co nanocrystal.Selection percentage makes it have seldom Au nanocrystal, thereby increases conductibility and do not hinder the operation of battery.

Figure 16 and Figure 17 represent two different templates 202, and it can have the matrix of affinity with work to the different nanocrystals of single element.In the example of Figure 16-Figure 18, form matrix 202, it contains Co is had the protein of affinity and in zone 204 Au had the protein of affinity in zone 206.Zone 206 and zone 204 are connected to one another, thereby form continuous template 202.Select the ratio in zone 206 and zone 204, thereby obtain the final required alloy of forming specifically.Yet, in metallurgical technology, provide compound or the alloy may be very difficult with specific Co and Au ratio, use template 202 can realize having the structure of AuCo of the through engineering approaches ratio of specific aequum, this template contains the different proteins that attracts and the nano particle of element-specific is had affinity.In the example of Figure 16, the ratio of this Co and Au is about 6: 1, and can easily obtain different proportion with the protein of different length, as shown in Figure 17.

Figure 18 represents to introduce the lithium ion battery that the high conductance gold atom reduces the resistance of electrode by ad-hoc location on film.As previously mentioned, these gold atoms use the through engineering approaches proteinaceous additive to film.

In the example of Figure 16 and Figure 17, template 202 is incorporated into the nanocrystal that single element is formed.Single element can be a metal, for example Au, Ag, Co, Li, C one of multiple semiconductor perhaps.Also can make up template, described template has the binding site with individual element in some positions, and have the binding site with binary compound in other positions, thereby the ternary compound of selected ratio is provided, this compound can obtain with standard alloy and/or molecular combinations method.

3. LED

Another embodiment of the invention relates to the improvement color control of Light-Emitting Diode.

Figure 19 represents the LED220 according to embodiment structure disclosed herein.This LED is included in the anode of first semiconductor regions 224 and at the negative electrode of second semiconductor regions 226, connects face 232 between them.Each electrode 22 and the terminal coupling that is connected in the diode of power supply Vs by wire 228 and wire 230.When consumption location 232 power supply that is passed in the face of connecing 232, according to the principles well-known of light-emitting diode from led lighting.

According to principle described herein, the color of light is through engineering approaches and have required wavelength specifically.This can realize by nano particle and their ratios separately of selecting to be present in anode 224 and negative electrode 226.Current, realize different colors by the semiconductor composition that changes integrated circuit.Http:// www.olympusmicro.com/primer/lightandcolor/ledsintro.html for example " depend on alloy composition, the bandgap range of III nitride devices from the 1.9eV indium nitride to 3.4eV gallium nitride (GaN) to the 6.2eV aluminium nitride.This emission wavelength ... change to green (390nm to 520nm) from purple is the function of indium content in the InGaN active layer." " color of light depends on the chemical composition of semiconductor integrated circuit to http://oemagazine.com/fromTheMagazine/jul01/ondisplay.html.

The short more luminous energy of the more little then wavelength of atom is high more, and it has zinc to mix or the wurtzite crystal structure usually, and it is derived from diamond lattic structure.Some are commonly used composed as follows: GaAs _xP _1-xGa _xLn _1-xPAl _xLn _1-xPAl _xGa _yLn _zPGa _xLn _1-xN.Have following target atom in prototype structure, can replace mutually, thus can regulate luminous color.”http://mrsec.wisc.edu/Edetc/IPSE/educators/leds.html.

Realize that in gas deposition the precision control that semiconductor is formed is very difficult, therefore forces the LED producer to use the classification again and the assessment technology of high price." LED has widely-dispersed brightness and color.Even all be such for single batch of product.Therefore classification again.”http://www.chml.com/led_laboratory.php

By the careful selection template, more closely distribution of color is arranged with the LED of digital alloy manufacturing.Because template can be blended in the solution exactly, the therefore composition of control template mixture accurately.Also can come the accurately composition of stationary digital alloy with the appropriate peptide sequence that comprises required ratio, and must the template that two or more are dissimilar not mix by design template.Further, digital alloy is at room temperature made in the solution in being contained in glass container, and this greatly reduces cost.

The example that various LED use is as follows:

http://mrsec.wisc.edu/Edetc/IPSE/educators/leds.html

http://www.ieee.li/pdf/viewgraphs_lighting.pdf

http://spiedl.aip.org/getabs/servlet/GetabsServlet？prog＝normal&id＝PSISDG005941000001594112000001&idtype＝cvips&gifs＝yes

http://www.lumileds.com/pdfs/techpaperspres/presentation_SAE％202004_kern.PDF

http://www.transporteon.com/Superlatives-L/LED.php

http://www.everlight.com/en_NewsDetail.asp？newsID＝200407001

Http:// www.nichia.com/product/phosphors.html and

http://www.mt-berlin.com/frames_cryst/descriptions/led_phosphors.htm

http://www.electrochem.org/publications/jes/samples/JES-H47_1.pdf

4. Intersheathes

Except special electronics and optical property, the mechanical performance of using digital alloy to improve material also can be favourable.As an example, the composition of interconnection material plays an important role to the mechanical strength of interconnection.When optimizing the composition of interconnect interface, form form between special metal, thus the bond strength of improvement interconnection, and also can improve diffusion property and make it have better long-time stability.On the contrary,, can form the intermetallic phase of fragility so, thereby cause the low interconnection of bond strength if the composition at interface is not well controlled.(for example see people J.Elect.Matls. such as Wu, Vol.34, No.11, p.1385; Lee and Subramanian, J.Elect.Matls., Vol.34, No.11, p.1399; People such as Tai, J.Elect.Matls., Vol.34, No.11, p.1357)

Figure 20 is presented at the intersheathes 250 that forms the interface between first conducting shell 254 and second conducting shell 258.In one embodiment, as described herein, intersheathes is based on digital alloy.The formation of this type of intersheathes can accurate be controlled at the composition and the position of the metal nanoparticle mixture at interface, and it provides the metal composition of control interconnection and the method for form, in order to the character of improvement interconnection.

Because nano particle has lower melting temperature than respective masses material, therefore intermetallic formation can appear at lower processing temperature.Nano particle is incorporated the suitable groups compound that appropriately concentrates in the micro-structural that interconnects into, and this also can be by alleviating strain at the place, grain boundary and preventing that dislocation from improveing the long-time stability of interconnection key.

As particular instance, the AuIn intersheathes at solder flux/backing plate interface works as diffusion barrier layer, and forbids the formation of fragility Au intermetallic phase.(for example, see people such as Wu, J.Elect.Matls., Vol.34, No.11, p.1385; Lee and Subramanian, J.Elect.Matls., Vol.34, No.11, p.1399; With people such as Tai, J.Elect.Matls., Vol.34, No.11, p.1357.) cost of In stops it to be widely used as the key component of unleaded solder.According to method as herein described, can concentrate higher In concentration at the interface, thereby form the intermetallic interface layer.Intermetallic form has direct influence to bond strength, and cylindricality (Cu _0.74Ni _0.26) ₆(Sn _0.92Ln _0.08) ₅The formation of intermetallic compound can cause better bond strength.Conventionally, these compounds by for example forming 150 ℃ of annealing in 500 hours.According to methods described herein, intermetallic compound is advantageously from suitably concentrating on the Cu of template _0.74Ni _0.26And Sn _0.92Ln _0.08Nano particle directly forms, especially because when forming between different metal form, and under the lower temperature aging condition, bond strength decline.

In this specification and/or list in the request for data table above-mentioned all United States Patent (USP)s, U.S. Patent Application Publication thing, U.S. Patent application, foreign patent, foreign patent application and non-patent application by reference integral body incorporate this paper into.

As mentioned above, describe specific embodiments of the present invention, its objective is, under the situation that does not deviate from the spirit and scope of the present invention, can carry out various modifications in order to illustrate although should be appreciated that this paper.Correspondingly, the present invention is unrestricted except that being subject to subsidiary claim.

Sequence table

＜110〉Cambrios Technologies Corporation

Yi Fulinhu

Angela Bel She Er

Xi Na closes

＜120〉digital alloy and manufacture method thereof

<130>191137.405PC

<140>PCT

<141>2007-05-18

<150>US?60/801,792

<151>2006-05-19

<150>US?11/679,726

<151>2007-02-27

<160>25

<170>FastSEQ?for?Windows?Version?4.0

<210>1

<211>16

<212>PRT

＜213〉artificial sequence

<220>

＜223〉can be transformed into or be assembled into the appropriate precursors albumen of amyloid fiber

<220>

＜221〉acetylation

<222>1

<400>1

Arg?Ala?Asp?Ala?Arg?Ala?Asp?Ala?Arg?Ala?Asp?Ala?Arg?Ala?Asp?Ala

1 5 10 15

<210>2

<211>12

<212>PRT

＜213〉artificial sequence

<220>

＜223〉can be transformed into or be assembled into the appropriate precursors albumen of amyloid fiber

<220>

<221>MOD_RES

<222>1

＜223〉biotin

<400>2

Arg?Gly?Asp?Ser?Lys?Gly?Gly?Gly?Ala?Ala?Ala?Lys

1 5 10

<210>3

<211>21

<212>PRT

＜213〉artificial sequence

<220>

＜223〉can be transformed into or be assembled into the appropriate precursors albumen of amyloid fiber

<400>3

Trp?Ser?Trp?Arg?Ser?Pro?Thr?Pro?His?Val?Val?Thr?Asp?Lys?Gly?Gly

1 5 10 15

Gly?Ala?Ala?Ala?Lys

20

<210>4

<211>18

<212>PRT

＜213〉artificial sequence

<220>

＜223〉can be transformed into or be assembled into the appropriate precursors albumen of amyloid fiber

<400>4

Ala?Val?Ser?Gly?Ser?Ser?Pro?Asp?Ser?Lys?Lys?Gly?Gly?Gly?Ala?Ala

1 5 10 15

Ala?Lys

<210>5

<211>9

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>5

Cys?Asn?Asn?Pro?Met?His?Gln?Asn?Cys

1 5

<210>6

<211>12

<212>PRT

＜213〉the unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>6

Leu?Arg?Arg?Ser?Ser?Glu?Ala?His?Asn?Ser?Ile?Val

1 5 10

<210>7

<211>9

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>7

Cys?Thr?Tyr?Ser?Arg?Leu?His?Leu?Cys

1 5

<210>8

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>8

Ser?Leu?Thr?Pro?Leu?Thr?Thr?Ser?His?Leu?Arg?Ser

1 5 10

<210>9

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>9

His?Asn?Lys?His?Leu?Pro?Ser?Thr?Gln?Pro?Leu?Ala

1 5 10

<210>10

<211>9

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>10

Cys?Asn?Ala?Gly?Asp?His?Ala?Asn?Cys

1 5

<210>11

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>11

Ser?Val?Ser?Val?Gly?Met?Lys?Pro?Ser?Pro?Arg?Pro

1 5 10

<210>12

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>12

Val?Ile?Ser?Asn?His?Arg?Glu?Ser?Ser?Arg?Pro?Leu

1 5 10

<210>13

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>13

Lys?Ser?Leu?Ser?Arg?His?Asp?His?Ile?His?His?His

1 5 10

<210>14

<211>8

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>14

Val?Ser?Gly?Ser?Ser?Pro?Asp?Ser

1 5

<210>15

<211>6

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>15

Ala?Glu?Glu?Glu?Glu?Asp

1 5

<210>16

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>16

Lys?Thr?His?Glu?Ile?His?Ser?Pro?Leu?Leu?His?Lys

1 5 10

<210>17

<211>8

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>17

Glu?Pro?Gly?His?Asp?Ala?Val?Pro

1 5

<210>18

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>18

His?Thr?His?Thr?Asn?Asn?Asp?Ser?Pro?Asn?Gln?Ala

1 5 10

<210>19

<211>15

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>19

Asp?Val?His?His?His?Gly?Arg?His?Gly?Ala?Glu?His?Ala?Asp?Ile

1 5 10 15

<210>20

<211>7

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>20

Lys?His?Lys?His?Trp?His?Trp

1 5

<210>21

<211>7

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>21

Arg?Met?Arg?Met?Lys?Met?Lys

1 5

<210>22

<211>7

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>22

Pro?His?Pro?His?Thr?His?Thr

1 5

<210>23

<211>9

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>23

Cys?Ser?Tyr?His?Arg?Met?Ala?Thr?Cys

1 5

<210>24

<211>9

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>24

Cys?Thr?Ser?Pro?His?Thr?Arg?Ala?Cys

1 5

<210>25

<211>12

<212>PRT

＜213〉unknown

<220>

＜223〉through identifying the peptide sequence that many semiconductors and metal material are had special affinity

<400>25

Leu?Lys?Ala?His?Leu?Pro?Pro?Ser?Arg?Leu?Pro?Ser

1 5 10

Claims (58)

1. composition comprises:

A plurality of templates, each template comprises at least one first binding site and at least one second binding site, described first binding site has the specificity binding affinity to first nano particle of first material, described second binding site has the specificity binding affinity to second nano particle of second material, and wherein said template comprises first binding site of x percentage and second binding site of y percentage through selection;

A plurality of first nano particles that are incorporated into first binding site separately;

A plurality of second nano particles that are incorporated into second binding site separately;

Wherein assemble described template, thereby make described first material and described second material with stoichiometric proportion x: y-shapedly become alloy.

2. composition as claimed in claim 1, wherein said first material is by A _mB _nThe compound of expression, described second material is by C _pD _qThe compound of expression, described alloy can be by (A _mB _n) _x(C _pD _q) _yExpression, wherein

A, B, C and D are the elements in the periodic table;

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n are not 0 simultaneously, and p and q are not 0 simultaneously.

3. composition as claimed in claim 2, wherein A, B, C, D are different elements, described alloy is a quaternary alloy.

4. composition as claimed in claim 2, wherein A, B are different elements with C, and D is identical with B, and described alloy is a ternary alloy three-partalloy.

5. composition as claimed in claim 2, n=q=0 wherein, described alloy is a bianry alloy.

6. composition as claimed in claim 2, wherein A, B, C and D are semiconductor element.

7. composition as claimed in claim 6, wherein A and C are IIIA family elements independently separately, and B and D are VA family elements independently separately.

8. composition as claimed in claim 7, wherein said alloy is Ga _xIn _1-xAs _yP _1-y

9. composition as claimed in claim 7, wherein said alloy is Ga _xIn _1-xN, Ga _xIn _1-xP or Al _xIn _1-xP.

10. composition as claimed in claim 2, wherein A and C respectively are IIB family elements, B and D respectively are VIA family elements.

11. composition as claimed in claim 2, wherein A, B, C and D are metallic elements independently separately.

12. composition as claimed in claim 1, wherein said template is a biological template.

13. composition as claimed in claim 12, wherein said first binding site is first peptide sequence, and described second binding site is second peptide sequence.

14. composition as claimed in claim 13, wherein said template are through through engineering approaches, consequently described first binding site and described second binding site are with controlled number with to each other apart from being distributed on the described template.

15. composition as claimed in claim 12, wherein said template is a protein, and described first peptide sequence and described second peptide sequence part that is described prlmary structure of protein.

16. composition as claimed in claim 15, wherein said protein are the variant of variant, S-layer protein or its genetic engineering or chemical modification of chaperonins or its genetic engineering or chemical modification or the variant of apoferritin or its genetic engineering or chemical modification.

17. composition as claimed in claim 13, wherein said template are the biological supports that merges described first peptide sequence and described second peptide sequence.

18. composition as claimed in claim 17, wherein said biological support are virion, bacteriophage, amyloid fiber or capsid.

19. composition as claimed in claim 1, wherein said template comprise the first kind template and second class template, described first kind template only has described first binding site, and described second class template only has described second binding site.

20. form the method for alloy, comprising:

Form at least one biological template, described template has at least one first binding site and at least one second binding site, described first binding site has the specificity binding affinity to first nano particle of first material, and described second binding site has the specificity binding affinity to second nano particle of second material;

Control described template, so that the number ratio of described first binding site and described second binding site is x: y (0＜x＜1,0＜y＜1);

Described first nano particle is combined with separately first binding site;

Described second nano particle is combined with separately second binding site; With

Formation comprises the alloy of described first material and described second material.

21. method as claimed in claim 20, wherein said first binding site is first peptide sequence, and described second binding site is second peptide sequence.

22. method as claimed in claim 20, wherein the control to described biological template comprises the described biological template of through engineering approaches, thereby expresses described first peptide sequence and described second peptide sequence in the precalculated position with scheduled volume.

23. method as claimed in claim 22, wherein said biological template is a protein.

24. method as claimed in claim 23, wherein said protein are the variant of variant, S-layer protein or its genetic engineering or chemical modification of chaperonins or its genetic engineering or chemical modification or the variant of apoferritin or its genetic engineering or chemical modification.

25. method as claimed in claim 23, wherein said biological template are the biological supports that merges described first peptide sequence and described second peptide sequence.

26. method as claimed in claim 25, wherein said biological support are virion, bacteriophage, amyloid fiber or capsid.

27. method as claimed in claim 20, wherein said first material is by A _mB _nThe compound of expression, described second material is by C _pD _qThe compound of expression, described alloy can be by (A _mB _n) _y(C _pD _q) _xExpression, wherein

A, B, C and D are the elements in the periodic table;

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n are not 0 simultaneously, and p and q are not 0 simultaneously.

28. composition as claimed in claim 27, wherein A and C are IIIA family elements independently separately, and B and D are VA family elements independently separately.

29. composition as claimed in claim 27, wherein A and C are IIA family elements independently separately, and B and D are VIA family elements independently separately.

30. composition as claimed in claim 27, wherein A, B, C and D are different elements, and described alloy is a quaternary alloy.

31. composition as claimed in claim 27, wherein A, B are different elements with C, and D is identical with B, and described alloy is a ternary alloy three-partalloy.

32. composition as claimed in claim 27, n=q=0 wherein, described alloy is a bianry alloy.

33. comprise the electrooptical device of alloy, described alloy comprises:

A plurality of templates, each template have more than first binding site and more than second binding site, and described template has the selected ratio of described first binding site to described second binding site;

With a plurality of first nano particle components of described more than first binding site coupling on the described biological template, described first component is made up of at least two different elements;

With a plurality of second nano particle components of described more than second binding site coupling on the described template, described second component is made up of at least two different elements, and at least one element of described second component is different with at least one element of described first component;

First binding site makes described template described more than first nano particle and described more than second nano particle can be assembled into described alloy to the selected number ratio of second binding site.

34. electrooptical device as claimed in claim 33, wherein said first nano particle is by A _mB _nThe compound of expression, described second material is by C _pD _qThe compound of expression, described alloy can be by (A _mB _n) _y(C _pD _q) _xExpression, wherein

A, B, C and D are the elements in the periodic table;

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n are not 0 simultaneously, and p and q are not 0 simultaneously.

35. electrooptical device as claimed in claim 34, wherein A, B, C and D are different elements, and described alloy is a quaternary alloy.

36. electrooptical device as claimed in claim 34, wherein A, B are different elements with C, and D is identical with B, and described alloy is a ternary alloy three-partalloy.

37. electrooptical device as claimed in claim 36, wherein A is that indium, B are that nitrogen and C are galliums.

38. electrooptical device as claimed in claim 37 wherein through selecting the ratio of described first binding site to described second binding site, makes alloy have In _xGa _1-xThe composition of N, x: (1-x), x is the atomic percent of InN in the described alloy.

39. electrooptical device as claimed in claim 34, n=q=0 wherein, described alloy is a bianry alloy.

40. electrooptical device as claimed in claim 33, the spacing between the wherein adjacent binding site is less than 10nm.

41. electrooptical device as claimed in claim 40, wherein first binding site is controlled by genetically engineered described template the ratio of second binding site.

42. electrooptical device as claimed in claim 33, wherein said alloy form first semiconductor material layer and second semiconductor material layer, and described electrooptical device also comprises:

First electrode with the described first semiconductor material layer coupling;

With second electrode of the described second semiconductor material layer coupling and

With the power supply of described first electrode and described second coupler electrode, thereby provide light-emitting diode.

43. solar battery structure comprises:

Semiconductor substrate;

With the photosensitive layer of described semiconductor substrate coupling, described photosensitive layer comprises alloy, and wherein said alloy comprises:

A plurality of templates, each template have more than first binding site and more than second binding site, and described template has the selected ratio of described first binding site to described second binding site;

With a plurality of first nano particle components of described more than first binding site coupling on the described biological template, described first component is made up of at least two different elements; With

A plurality of second nano particle components with described more than second binding site coupling on the described template, described second component is made up of at least two different elements, at least one element of described second component is different from least one element of described first component, described first binding site through selecting to the number of described second binding site than making described template described more than first nano particle and described more than second nano particle can be assembled into described alloy.

44. solar battery structure as claimed in claim 43, wherein said first nano particle is by A _mB _nThe compound of expression, described second material is by C _pD _qThe compound of expression, described alloy can be by (A _mB _n) _y(C _pD _q) _xExpression, wherein

A, B, C and D are the elements in the periodic table;

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n are not 0 simultaneously, and p and q are not 0 simultaneously.

45. solar battery structure as claimed in claim 44, wherein A and C respectively are selected from the III family or the II family of the periodic table of elements, and B=D also is selected from the V family or the VI family of the periodic table of elements respectively.

46. solar battery structure as claimed in claim 45, wherein A and C respectively are selected from the III family of the periodic table of elements, and B is selected from the IV family of the periodic table of elements.

47. solar battery structure as claimed in claim 45, wherein A is that gallium, B are that indium and C are nitrogen.

48. solar battery structure as claimed in claim 45, wherein A is that aluminium, B are that gallium and C are arsenic.

49. solar battery structure as claimed in claim 44, wherein A is that indium, B are that phosphorus, C are that aluminium and D are nitrogen.

50. structure as claimed in claim 44, wherein A is that aluminium, B are that arsenic, C are that gallium and D are indiums.

51. structure as claimed in claim 44 also comprises:

With second photosensitive layer of described photosensitive layer coupling, described second photosensitive layer comprises second alloy, described second alloy by (A ' _{M '}B ' _{N '}) _{Y '}(C ' _{P '}D ' _{Q '}) _{X '}Expression, wherein

A ', B ', C ' and D ' are the elements in the periodic table;

0≤m '≤1; 0≤n '≤1; M '+n '=1; With

0≤p '≤1; 0≤q '≤1; And p '+q '=1, prerequisite is that m and n are not 0 simultaneously, and p and q be not 0 simultaneously, and prerequisite is that at least one of A ', B ', C ', D ', x ', y ', m ', n ', p ' and q ' is different from A, B, C, D, x, y, m, n, p and q respectively.

52. lithium ion battery comprises:

Anode comprises cobalt, oxygen and is selected from gold, copper and silver-colored low resistive metal basically that described low resistive metal optionally is controlled at less than 4 the ratio of cobalt, and is placed in the described anode, thereby reduces the cell resistance of described battery;

Negative electrode; With

Be placed on the electrolyte that transmits lithium ion between described anode and the described negative electrode,

Wherein said cobalt and low resistive metal form existing under the situation of a plurality of templates, each template has a plurality of and cobalt has first binding site of affinity and second binding site that a plurality of and described low resistive metal has affinity, the binding site number of described low resistive metal is less than the binding site number of described cobalt basically, and has first and second binding sites of selected ratio.

53. lithium ion battery as claimed in claim 52, wherein said template is a biological template, template, thus it can be through genetically engineered position and the amount of controlling described first and second binding sites.

54. lithium ion battery as claimed in claim 52, wherein the described low resistive metal of higher concentration is located at adjacent electrode and is connected, rather than is located at the anode region near the outer end.

55. lithium ion battery as claimed in claim 52 also comprises:

Negative electrode, it comprises carbon and is selected from the low resistive metal of gold, copper and silver basically that described low resistive metal optionally is controlled at less than 1 the ratio of described carbon, and is placed in the described anode, thereby reduces the cell resistance of described battery.

56. structure comprises:

First conducting shell;

Second conducting shell; With

Be placed on the intersheathes between described first conducting shell and described second conducting shell, the formation of described intersheathes is by forming at least one biological template, described biological template has at least one first binding site and at least one second binding site, described first binding site has the specificity binding affinity to first nano particle of first material, described second binding site has the specificity binding affinity to second nano particle of second material, control described template, so that described first binding site is x: y (0＜x＜1 with the quantity ratio of described second binding site, 0＜y＜1), described first nano particle is combined with separately first binding site, described second nano particle is combined with separately second binding site; Comprise the alloy of described first material and described second material with formation.

57. structure as claimed in claim 56, wherein said first material is by A _mB _nThe compound of expression, described second material is by C _pD _qThe compound of expression, described alloy can be by (A _mB _n) _y(C _pD _q) _xExpression, wherein

A, B, C and D are the elements in the periodic table;

0≤m≤1; 0≤n≤1; M+n=1; With

0≤p≤1; 0≤q≤1; And p+q=1, prerequisite is that m and n are not 0 simultaneously, and p and q are not 0 simultaneously.

58. structure as claimed in claim 57, wherein A, B, C and D are metals independently separately.

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