CN1762000A - Production of nanoparticulate thin films - Google Patents

Production of nanoparticulate thin films Download PDF

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Publication number
CN1762000A
CN1762000A CN 200480007446 CN200480007446A CN1762000A CN 1762000 A CN1762000 A CN 1762000A CN 200480007446 CN200480007446 CN 200480007446 CN 200480007446 A CN200480007446 A CN 200480007446A CN 1762000 A CN1762000 A CN 1762000A
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China
Prior art keywords
film
matrix
particle
nano
protein
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CN 200480007446
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Inventor
迈克·佩里
杰伊·霍伊维勒
詹姆斯·M·霍利亨
阿图尔·纳托斯基
埃里奇·梅斯
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NanoMagnetics Ltd
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NanoMagnetics Ltd
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Publication of CN1762000A publication Critical patent/CN1762000A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/62—Record carriers characterised by the selection of the material
    • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
    • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
    • G11B5/712—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the surface treatment or coating of magnetic particles
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/842—Coating a support with a liquid magnetic dispersion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/009—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity bidimensional, e.g. nanoscale period nanomagnet arrays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/005—Thin magnetic films, e.g. of one-domain structure organic or organo-metallic films, e.g. monomolecular films obtained by Langmuir-Blodgett technique, graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/007—Thin magnetic films, e.g. of one-domain structure ultrathin or granular films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A method of forming a magnetic recording device having a film of magnetisable nanoparticles, which comprises preparing a suspension of magnetisable nanoparticles in a carrier fluid and depositing said fluid suspension onto a substrate surface as droplets having a volume less than about 1 nl to form said film of magnetisable nanoparticles as a dry residue of the deposited fluid suspension.

Description

The preparation of nanoparticulate thin films
Invention field
The present invention relates to a kind of ink jet printing thin films of using.The film that obtains can be used for multiple application, for example as the ingredient in magnetic medium and the semiconductor medium.
Background of invention
A lot of methods can be used for preparing film, for example, chemical vapour deposition technique, molecular beam epitaxial growth method, evaporation method, sputtering method and spin-coating method (" Handbook of Thin Film Materials:Vol.1 Deposition and processing of thin films " 2002 Ed.Nalwa H.S., Academic Press; " Thin Films on Glass " 1997 Eds.Bach Kraus, Springer-Verlag).Sputtering method and electronics-evaporation method have become the preferred for preparation method of being recommended that is used for the disc driver magnetic medium in computer industry traditionally.
The preparation of self-assembled protein array has caused extensive concern, because this array provides multiple application in contemporary nanometer technology, for example as semiconductor device and biology sensor (YunS C et.Al.2001, MRS Symposium Proc.j2.3/1-j2/3/6; McMillan A et.Al.2002 NatureMaterials 1 (4) 247-252).The method that forms protein film mainly concentrates on two-stage method and prepares film.At first, the 2-D protein array is formed on the liquid film.Then these films are transferred on the solid state substrate, for example on the silicon wafer.Langmuir-Blodgett technology (BrittD W et.Al.Phys.Chem.Chem.Phys.2000 2 4594-4599) is known membrane preparation technology, and it is included in lipid-air interface and forms protein array.Many other methods based on this basic mechanism also are disclosed, for example at air-water interface (Kobayashi K et.al.2001Biosci.Biotechnol.Biochem.65 (1) 176-179), mercury-air interface and liquid-air interface (Nagayama K et.al.1995 Jpn J Appl.Phys.34 pages 3947-3954) and gallium-aqueous solution interface (Adachi E et.Al.1998 Chem.Phys.Lett.284 440-445) preparation self-assembled protein array.Protein film also can form (Goodall S et.al.2002 J.Aerosol Med.15 (3) pages 351-357) by spraying process and vapour deposition process.
In the detection industry, discrete unit (Roda A et.al.2000 Biotechniques 28 (3) pages492-496 that deposit specified protein by ink jet printing method on solid state substrate are disclosed; WO 96/22533).Herein, its purpose is the array of the individual proteins that obtains to fix, and it can be used for screening single target.Ink jet printing method is that the computer derivation information is printed to routine techniques (Calvert P 2001 Chem.Mater.13 3299-3305) on the paper.But the single point tactical deployment of troops can be used for many fields, and other application examples such as magnetic recording need very smooth and continuous films.
We now are surprised to find, and ink jet printing method is a kind of magnetic particle that forms protein, magnetic particle and encapsulated by macromolecular material to small part and the effective technology of semi-conductor nano particles film.
Summary of the invention
First aspect of the present invention provides a kind of formation to have the method for the magnetic recording system of magnetisable film of nanoparticles, comprise the suspending liquid of the magnetisable nano particle of preparation in carrier fluid, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, formed the described film of magnetisable nano particle as the dry residue of deposits fluid suspending liquid.
Second aspect of the present invention provides a kind of method that forms magnetisable film, comprise the suspending liquid of the magnetisable nano particle of preparation in carrier fluid, wherein each magnetisable nano particle all is formed in the protein housing to small part, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described magnetisable film as the dry residue of deposits fluid suspending liquid.
The 3rd aspect of the present invention provides a kind of method that forms the inorganic nano-particle film on matrix, comprise the suspending liquid of preparation inorganic nano-particle in carrier fluid, wherein each inorganic nano-particle all is formed in the protein housing to small part, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described film as the dry residue of deposits fluid suspending liquid.
The 4th aspect of the present invention provides a kind of method that forms protein film on stromal surface, the thickness of described protein film is less than about 10 times of the sub-diameter of component protein plasmid that spreads all over whole film substantially, described method comprises the suspending liquid of preparation protein granule in carrier fluid, described protein granule has carried out membrane filtration step, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described film as the dry residue of deposits fluid suspending liquid.
The 5th aspect of the present invention provides a kind of magnetic recording system with magnetisable film of nanoparticles, wherein said particle has prepared in the suspending liquid of carrier fluid, and deposit to stromal surface less than the droplet form of about 1nL with volume, obtain the described film of magnetisable nano particle as the dry residue of deposits fluid suspending liquid.
Description of drawings
In order further to set forth the present invention, will carry out non restrictive description to embodiment with reference to the accompanying drawings.In the accompanying drawings:
Fig. 1: the ink-jet printing apparatus that its mesostroma is placed by vertical direction.
Fig. 2: matrix locating device in first matrix-disengaging configuration and second matrix-position of engagement.
Fig. 3: wherein mandrel is positioned at the ink-jet printing apparatus of retracted position.
Fig. 4: the ink-jet printing apparatus that its mesostroma is placed by horizontal direction.
Fig. 5: the ferritin that is deposited on the glass matrix raps the AFM figure of pattern.
Fig. 6: the ferritin on the glass matrix that is deposited on (a) not radiation exposed glass matrix and (b) is crossed by the UV photoirradiation raps the AFM figure of pattern.
Summary of the invention
Ink jet printing method comprises the Xiao amount Ye that will usually be less than the Ya millilambda by a plurality of ultra micro nozzles Attitude Wu Zhi deposits on the matrix. Usually, deposition process comprises that the Ya electricity of printing nozzle is auxiliary or hot Auxiliary operation. The amount of every deposit liquid is usually greater than Yue 0.1 picoliter, for example greater than Yue 1 Picoliter. But Yue 1 millilambda of this amount Xiao Yu, Yue 100 picoliters of for example Xiao Yu or Xiao Yu Yue 10 Picoliter. Aspect the Zai You Xuan of the present invention, Yue 3 picoliters of the amount of every deposit fluid Wei.
Nozzle-the sedimentation of picoliter quantity of material can be controlled well and be deposited on the set district of matrix The volume of the upper Wu Zhi of Yu. Zai will be before matrix contacts, and the Zhi amount that Ye drips equals on the inkjet nozzle The drop mass that exists. Replacedly, single Ye dripped and can be subdivided into more before Zai contacted Yu matrix The Ya Ye of Xiao drips " spraying ". When the Zai droplet-shaped became the spraying of Zhe Yang, its Xing can be to a great extent Depend on that size that initial Ye drips and shower nozzle are Yu the distance between matrix. Ye drips degree Yi time that Xi divides Determined the capped zone of matrix. The Xi hole that ink jet printing method provides can the control of higher degree ground The nano particle Xiao that ink-jet processed produces drips.
In addition, ink-jet printing technology can be compound to the standby process Zhong of industrial Zhi easily, and Yu Slot type application system Xiang ratio may Xu Yao with regard to the Chong amount of base material per unit area coating material Yuan material still less.
When particle is magnetic nano-particle, but they are encapsulated in big molecule housing Zhi small part Zhong. Replacedly, magnetic nano-particle can be not packed. Zhe Xie particle can pass through this area skill The known method of art personnel comes Xing to become, and method for optimizing produces suitable size and decentralization control. Zai one aspect of the present invention, magnetic nano-particle Xing become for example protein of the big molecule housing of Zai Zhong. This housing can be removed subsequently, for example by laser pyrolysis processes, stays not packed magnetic The Xing nano particle. But magnetic nano-particle also Xing becomes the subsequently also surfactant that can be removed of Zai Micella Zhong, for example by surfactant solution Xi being released the Xia Zhi critical concentration Yi, advance then Hang filters.
When the non magnetic particle of particle Wei, semi-conductor nano particles for example, but they are Zhi small part Encapsulated by the protein housing. Selectively, but their Xing become the Zai subsequently can be by for example LASER HEAT In the encapsulation protein housing that solution is removed, stay not packed non magnetic nano particle.
Magnetic recording media is to have magnetic and any medium that can storage data.Preferably, but without limits, recording medium can be present in the hard disk drive, for example is used for computer, audio frequency apparatus, automobile, video recording equipment etc.In addition, medium also can be used for tape or magnetic card device.
Aspect more of the present invention, magnetic recording system preferred data storage capacity is preferably greater than the 5Gb/ square inch greater than the 1Gb/ square inch, more preferably greater than the 10Gb/ square inch with most preferably greater than the 20Gb/ square inch.
Being used for ink-jet printing apparatus of the present invention suitably comprises: the storage pool that (i) holds coating particle; (ii) ink gun; The conduit that (iii) connects storage pool and ink gun; (v) make matrix to be coated remain on the support component of firm position; (vi) make ink gun and matrix ask the device that relatively moves; (vii) control ink gun and matrix and ask the control device that relatively moves, for example computer software.Choose wantonly in the pipe line that connects storage pool and ink gun and can comprise valve.
Ink gun suitably comprises (i) entry port usually successively; The (ii) storage pond part of coating particle suspending liquid; (iii) a plurality of nozzles with hole of preliminary dimension, preferably each nozzle comprises littler storage pond part; (iv) from the mechanical hook-up of nozzle ejection wash coat suspension drop.
The various systems of spraying ink droplet are known, mainly contain piezoelectric method, hot method, electrostatic method and acoustic method (Le HP 1998 J.Imaging Sci.Tech.42 49-62).For example in the bubble type ink jet printing head, each nozzle unit includes heating element.When component temperature is increased to hundreds of temperature fast, just produce and impel the bubble of drop by nozzle, these bubbles have replaced liquid ink.In the piezoelectricity deposition, be applied to the electric field that is positioned on the whole piezoelectric crystal of nozzle and cause crystal modification, thereby reduced the volume of the nozzle that is used for liquid, and drop is discharged from the aperture, nozzle wherein is generally pottery.Any one of said system all can be used for the present invention.
When operation is applicable to ink-jet coating unit of the present invention, particle suspension is applied on the matrix by ink gun.In preferred embodiment, the ink gun nozzle is placed with basic vertical with stromal surface.In deposition process, matrix and ink gun move relative to each other, and need regions coated thereby ink gun can be applied to matrix with particle suspension.This relatively moves and can realize by moving of ink gun, also can by matrix move or both all move and realize.If desired, the distance between also adjustable integral basis matter surface and inkjet nozzle.In the scope that this those of ordinary skills of being adjusted at can realize.
Matrix optimization is circular, but can be the Any shape that is suitable for set application.
In one aspect of the invention, stromal surface is preferably smooth as far as possible.Stromal surface needn't be the plane in its whole zone, but should not have partial discontinuous basically.With regard to surfaceness, average surface roughness R aPreferably less than about 1nm, for example about 0.1nm.R aBe by finding the average centerline parallel to determine with the surface.Any paddy that is lower than center line transformed with the peak calculate.The average height that is higher than the peak (comprise conversion after paddy) of center line is mean roughness R aThe mean roughness of stromal surface can determine by well known to a person skilled in the art technology, for example, and by contour curve mensuration, elliptic polarization method or atomic force microscopy or its combination.For example, can use atomic force microscopy.
The present invention interchangeable aspect, matrix has bigger roughness.For example, the average surface roughness R of matrix aGreater than about 1nm, be preferably greater than about 5nm.Aspect this, surfaceness R aPreferably less than about 30nm, for example less than about 20nm or about 10nm.Found in some embodiments of the present invention, can obtain between matrix and coating particle bigger bonding by the coarse average-size of control surface.
Matrix also preferably has high skin hardness, and for example, Vickers (Vickers) hardness is preferably greater than about 700kg/mm greater than about 600kg/mm.Wish that also matrix has high stiffness, for example elastic modulus is greater than about 70Gpa, is preferably greater than about 80Gpa and more preferably greater than about 90Gpa.Matrix also can have the characteristic modulus greater than about 25Gpa, for example greater than about 30Gpa or greater than about 35Gpa.It is favourable that matrix has low thermal expansivity, because this has improved the readability by the pen recorder of coating substrate preparation.Thermal expansivity is preferably less than 30ppm K -1, for example less than 20ppm K -1In particularly preferred embodiments, the thermal expansivity of matrix is less than 10ppm K -1In the preferred embodiment of the present invention, matrix has low heat conductivity.This coating substrate that raise can be by effectively as the temperature of magnetic recording system.Therefore, the preferred matrix heat conductivity of the present invention is less than 20Wm -1K -1, for example less than 10Wm -1K -1Or less than about 5Wm -1K -1Suitably examples of material is a glass, for example from Ohara Inc Japan (15-30, Oyama 1-Chome, Sagamihara-Shi, Kanagawa, 229-1186 Tel:(81) 42-772-2101, Fax:(81) 42-774-1071, http: the TS-10SX of Gou Maiing ∥ www.ohara-inc.co.jp), and aluminium.When material was aluminium, the compound of the inferior phosphorus of its available Ni-applied.
In an embodiment of the invention, matrix is vertically placed, and makes ink gun and described matrix (1) homeotropic alignment, as shown in Figure 1.A face homeotropic alignment of at least one ink gun (2) and matrix.In another embodiment, device can comprise that at least one is placed on the ink gun on any face of described matrix.Matrix is around mandrel (3) (axle X) rotation, and inkjet head device keeps static simultaneously.Replacedly, matrix can remain on rest position, and ink gun is around axle " X " rotation or mobile in parallel with substrate plane basically single plane " Y ".The present invention preferred aspect, matrix and ink gun move simultaneously.For example, the matrix rotation, inkjet head device is around axle " X " rotation or mobile in plane " Y " simultaneously.When matrix phase rotated for ink gun, angular velocity of rotation can be regulated with the control device that the ink gun radial position changes by control, was remained unchanged substantially by the matrix areas that ink gun covers guaranteeing.Typical matrix is discoidal.
Before coating, the matrix disk is arranged on the mandrel of ink-jet coating unit, as shown in Figure 1 and Figure 4.Fig. 2 represents to comprise the suitable positioning equipment of domes (2), and wherein single clamping element (3) is radial outstanding from described domes.In first position (Fig. 2 b), the engagement of the outer rim of each element and disk (1).And these elements remain in the domes disk, and make it accurately move to the position that is positioned on the mandrel.After disk was arranged on the mandrel, clamping element can break away from from the disk wheel rim, shown in Fig. 2 a.Clamping element can be structure that spring for example forms or along the retractible solid-state nail of its longitudinal axis.
In order to make disk be arranged in the ink-jet coating unit, the mandrel of support disk (3) can be withdrawn into primary importance by control device (4).The matrix disk is movable to the position that is positioned at coating unit then, as shown in Figure 3.Disk is placed in the coating unit, and the longitudinal axis that makes the center, hole of disk and regracting mandrel in line.Retractible mandrel can be inserted into the center pit of disk then.Then disk is clamped securely on the mandrel.Those skilled in the art can clear and definite disk clamp device for example packing ring etc. can be used by mechanical type, to guarantee that disk is fixed in the plane vertical with the mandrel longitudinal axis fully, thereby when mandrel rotates with desired speed, disk will rotate and remain on its position that is positioned at single plane.For example, mandrel can have the extended xsect of energy, thereby it can expand to be full of the center pit of disk, guarantees that it is in the upright position.Those skilled in the art's easy to understand can be used for rotating the multiple device of mandrel.
In another embodiment as shown in Figure 4, matrix can be fixed on the basic mandrel in surface level.Ink gun (1) is arranged to matrix (2) top, and can move in the direction parallel with plane " X ".In operation, matrix is around the rotation of mandrel (3) " X " axle, and inkjet head device keeps static simultaneously.Replacedly, matrix remains on rest position, and ink gun moves in basic parallel with stromal surface plane " X ".The present invention preferred aspect, matrix and ink gun move simultaneously.For example, the matrix rotation, inkjet head device moves in " X " plane simultaneously.
In operation, be positioned at predetermined coated position in case those skilled in the art will appreciate that matrix, its should with holding device for example mandrel mesh securely." firmly " speech is meant that matrix does not depart from its position in single plane basically, thereby ink jet printing can proceed to needed degree of functioning, and can not destroy ink gun or matrix.
Be used for device of the present invention, those skilled in the art can understand the size of ink gun and can select according to concrete application.For example, but designs fix at the ink gun of rest position, some embodiments of for example above-mentioned Fig. 1 and equipment shown in Figure 4, thereby the diameter of the disk that its longitudinal size is substantially equal to want coated.In addition, be used in the number of nozzle in the concrete shower nozzle by being determined by the surface area that ink gun covers.The number that those skilled in the art can clear and definite nozzle and the size of nozzle can be according to specifically should being used for design, and can make up the ink-jet coating unit that can alternately hold different shower nozzles.
Various aspects of the present invention preferred embodiment in, matrix is handled to promote the dispersion thereon of coated particle suspending liquid.This processing can comprise chemistry, machinery or radiation treatment or its combination.For example, chemical treatment can comprise the use wetting agent, for example pure, penta-1-alcohol or use dispersant/for example, NP40 (Accurate Chemical and Scientific, Westbury, NY 11590US for example, Tel:(516) 333-2221 (800) 645-6264, Fax:(516) 997-4948).Before coated particle suspending liquid, spreading agent can be coated on the matrix.Replacedly, spreading agent and/or wetting agent can be added to and will form on matrix in the suspending liquid that contains particle of film.The wetting agent that the optimized coatings of matrix is required or the amount of spreading agent depend on concrete dispersion liquid, but addition preferably can not cause the surface tension at nozzle bore place to be reduced to the value that is not enough to keep nozzle inner suspension liquid when the additional jet power in the ink gun does not exist.
In some embodiments of the present invention, before coating, stromal surface is carried out pre-service.This can be undertaken by for example mechanical treatment or radiation treatment.Mechanical treatment can comprise cleaning substrate, for example by the chemical-mechanical polishing method.Radiation treatment preferably includes and places ultraviolet ray down matrix.
The pretreating agent source is usually located in the plane identical with injector head (4).Disk usually shown in direction (arrow) rotation, and pretreating agent for example irradiation beams or chemical wettability agent contacted with matrix before matrix places under the ink gun.The time interval and coating between pretreated duration and pre-service depend on application.For example, pretreating agent source and ink gun can be operated basically simultaneously, thereby pre-service comprises the only one way that makes disk pass through target area, pretreating agent source.In other embodiments, a plurality of one way of disk by target area, pretreating agent source can take place in matrix areas.Before depositing to particle on the matrix, passed through a period of time at interval by ink jet printing.
Preferably use equipment as shown in Figure 1, it comprises ink gun and the ultraviolet source that is placed in the plane that is parallel to each other substantially, making that ink gun is vertical with matrix basically places, and the light beam that send ultraviolet light source (4) is basically in also vertical with matrix plane.
Also can handle after particle deposits on the matrix, for example solidify or be exposed to IR light or undertaken by heating by UV-to film.Film also can be annealed after particle deposition, for example by in the conventional annealing stove, heat matrix to temperature at least about 300 ℃ or by being exposed in the laser beam.When film will be as the element in the magnetic recording system, particularly preferably be film is annealed, because this can greatly improve the magnetic property of film.
Of the present invention many aspect, for example be used for the magnetic nanometer film of magnetic recording media, the surface of film is preferably smooth as much as possible and smooth.The surface of film needn't be definitely smooth in its whole zone, but because the effect that closes on of reading head in the operation, the surface of film should not have partial discontinuous basically.For example, at the lip-deep discontinuous height of magnetic surface that preferably is higher than of film less than about 13nm.This is illustrated under the situation of sealing the magnetic nano-particle in the apoferritin housing up for safekeeping, and the diameter (comprise and seal housing up for safekeeping) that the degree of admission of discontinuous size is about a particle in the film surface is with effectively as magnetic recording media.
Also preferred, film thickness is not more than 2 diameters (comprising any housing of sealing up for safekeeping) that spread all over the particle of whole film substantially, particularly when matrix is smooth relatively on the coated particle length scale.
Therefore, one of the present invention preferred aspect, film is essentially continuous monofilm form.Film should be continuous basically, and to reduce the discontinuous generation of film thickness, this can produce coating zone and uncoated interregional interface continuously.
For example, we can carry out magnetic recording on magnetisable device, be included in the magnetic nano-particle of average surface roughness Ra less than encapsulation ferritin on the matrix of about 1nm, wherein the variation of film thickness is about 25nm (diameter of single ferritin particle is about half of this value) on matrix.
In other aspects of the present invention, when film is not used as magnetic storage medium, can be looser to the requirement of film surface smoothness.Required film smoothness depends on concrete application, but in certain aspects, for example, the average surface roughness of film is not more than about 10, for example is not more than about 5 or be not more than about 3 or 2 particle diameters (comprising any encapsulating housing).
Because matrix has different roughness according to various aspects of the invention, so the film thickness of promptly fixing a point on the film surface is somewhat dependent upon the surfaceness of substrate matrix.Therefore aspect more of the present invention, the variation of film thickness on the degree of depth is not more than about 10 times (comprising any encapsulating housing) of the component particle diameter that spreads all over whole film substantially, more preferably no more than about 5 times and most preferably be not more than about 3 or 2 times of particle diameter of particle diameter.The absolute thickness of film depends on the diameter of particle, but film thickness prepared in accordance with the present invention is usually less than about 500nm, is more preferably less than about 100nm and most preferably less than about 50nm.In the particularly preferred embodiment of the present invention, the film thickness that spreads all over whole film is less than about 30nm.
A kind of when magnetic or magnetizable nano particle are deposited to the method for preparing magnetic recording system on the base material with volume less than the droplet form of about 1nL when the present invention relates to, for example by ink jet printing method, magnetic particle wherein can be packed or not packed.
Under the packed situation of particle, encapsulating material can comprise organic material or inorganic material, for example siloxane, silane or derivatives thereof.Term " encapsulation " is meant with macromolecular material and applies or be formed on particle in the predetermined hole of macromolecular material.Encapsulating material can be a continuous meta structure, for example, comprises the oligomeric protein of a plurality of polypeptied chains.Replacedly, a meta structure that encapsulating material can separate exists, and it encases inorganic material to small part, and it keeps abreast of but separated structures, or forms multiple component structure with adjacent structural interaction.
Encapsulating material can comprise one-component or coefficient various ingredients, and holding nuclear core magnetic nano-particle, the diameter of particle when nonspherical particle (or maximum gauge) preferably is not more than about 100nm.Preferred diameter is not more than about 50nm, and more preferably it is about 20nm or littler.This size to small part is determined by the size of encapsulating material.Replacedly, encapsulating material can comprise the suitable opening that is not encased fully, but it can still receive and carry magnetic particle; For example, perforate can be limited by big intramolecular anchor ring.
The present invention relates to form magnetisable film and magnetic recording system aspect, the magnetisable nano particle of nuclear core should be too not little so that can not keep ferromagnetism at ambient temperature.Environment temperature for example is higher than about 15 ℃ usually above about 0 ℃.Environment temperature is usually less than about 50 ℃, for example is lower than about 30 ℃.This shows that when operating at ambient temperature, magnetisable nano particle is usually greater than 2nm.
In preferred embodiment, encapsulating material can be organic macromolecule, and molecular weight is up to about 1500kD, usually less than about 500kD, wherein organic macromolecule we be meant the assembly of molecule or molecule.This class organic macromolecule can be surfactant, polymkeric substance or protein.
When the present invention relates on matrix magnetisable film of preparation or inorganic nano-particle film, described particle to small part is formed in the encapsulation protein housing, but can be packed or not packed during deposition on matrix.When inorganic nano-particle was semi-conductor nano particles, preferred these particles of some embodiments of the present invention deposited on the matrix with the form that does not encapsulate, because this can produce the more semiconductor film of high storage density.
The present invention relates to the various aspects of protein, protein can comprise artificial protein, for example recombinant protein from natural or obtain from other source.
In some preferred implementations of the present invention first, second and the third aspect, protein is as encapsulating material, and it encases inorganic particulate to small part.In preferred embodiment, inorganic particulate comprises magnetic metal or metal alloy, or semiconductor material.
In the embodiment aspect the 5th of the present invention, in the forming process of film on matrix, protein does not combine with other material at least.
Be applicable to that protein of the present invention comprises flagellum L-P ring, antibiotic, chaperoninins for example bacterium GroEL and GroES, DPS and capsid virus.For example, DPS is ferritin autoploid, dodecamer DNA protected protein matter, and it is included in the hollow on the triad.Flagellum L-P ring is the loop configuration of about 13nm of internal diameter and the about 20nm of external diameter.They can be induced and be concentrated row in a row neat and extend several microns display, and about 13nm is thick.Under rarer concentration, dimer can form the thick array of about 26nm.
In relating to the highly preferred embodiment of the present invention of protein, protein is a member in the ferritin family.The present invention most preferably uses iron storage albumen, ferritin, utilizes its inner cavity to prepare the nano grade inorganic particle.The molecular weight of ferritin is 450kD.Ferritin is used in all to be had in the interior iron metabolism of life species, and its structure is retained in wherein well.Its substate unit by 24 self assemblies is formed, so that the mesopore housing of the about 12nm of external diameter to be provided.Housing has the hole that diameter is 8nm, and it stores iron (III) atom of about 4500 paramagnetism hydrated ferric oxide forms usually.This hydrated ferric oxide can be removed (not having the ferritin of hydrated ferric oxide to be called as " apoferritin "), and can compound other material.Substate in the ferritin is arranged closely; But on 3-solid axle and 4-solid axle, the passage that enters the hole is arranged.
The preferred protein that is used in the various aspects that the present invention relates to protein is an apoferritin, and it has the hole that diameter is about 8nm.
Ferritin can natural existence in vertebrate, invertabrate, plant, Mycophyta, yeast, bacterium.Also can be by the synthetic preparation of recombinant technique.These synthetic forms can be identical with natural form, although also may synthesize the mutant form, these mutant forms still can be retained in the key property that its inner cavity holds particle.The purposes of the natural and synthetic form of all these of ferritin is all in protection scope of the present invention.
Nitrogen flow down by the buffering sodium acetate solution in the dialysis ferritin is transformed into apoferritin.Can remove hydrated ferric oxide nuclear core by for example using the reduction chelation of thioglycolic acid.It can examine core by the hydrated ferric oxide that repeats to dialyse to remove reduction fully from solution subsequently in sodium chloride solution.Hole under the apoferritin relaxation state is about 8nm.The diameter of nuclear core nano particle (that is, having removed the nuclear core material of encapsulating material) can reach about 15nm, because protein is extensible to hold the bigger particle of diameter greater than 1 8nm.
In the different aspect that the present invention relates to the formation of magnetic nano-particle film, can comprise ferromagnetic metal by packed or not packed magnetic nano-particle, for example cobalt, iron or nickel; Metal alloy; Rare earth metal and transition metal alloy; M-type or spinel ferrite.Metal or metal alloy can comprise one or more following materials: aluminium, barium, bismuth, cerium, chromium, cobalt, copper, dysprosium, erbium, europium, gadolinium, holmium, iron, lanthanum, lutetium, manganese, molybdenum, neodymium, nickel, niobium, palladium, platinum, praseodymium, promethium, samarium, strontium, terbium, thulium, titanium, vanadium, ytterbium and yttrium or its be potpourri arbitrarily.
Preferred described magnetic nano-particle comprises bianry alloy or ternary alloy three-partalloy, for example cobalt-nickel, iron-platinum, cobalt-palladium, iron-palladium, samarium-cobalt, dysprosium-iron-Turbide (turbide) or neodymium-iron bromide, iron-cobalt-platinum, cobalt-nickel-platinum or cobalt-nickel-chromium.More preferably, described nano particle comprises cobalt or platinum or its alloy, for example alloy of cobalt and platinum.
In the preferred implementation of the present invention aspect first, magnetic nano-particle is encapsulated by protein material.
In the preferred implementation of third aspect of the present invention, magnetic nano-particle or semi-conductor nano particles that particle is encapsulated by protein material.In the embodiment of the present invention aspect this, magnetic particle comprises by the cobalt/platinum alloy or the iron/platinum alloy of apoferritin or DPS encapsulation.
Magnetic nano-particle can prepare by the following method, wherein encapsulating material for example organic macromolecule usually the suspending liquid in water-bearing media combine with the ion gun of proper metal, constitute nuclear core magnetic nano-particle.In the method, the preferable alloy ion gun is joined in the encapsulating material source gradually.For example, the kation and the negative ion source that can add capacity provide kation and the negative ion source of the each circulation of each encapsulating housing more than 1 atom, and kation and the negative ion source of the each circulation of each encapsulating housing more than 20 atoms preferably are provided.Can add the kation of capacity and kation and the negative ion source that negative ion source provides the each circulation of each encapsulating housing to be less than 200 atoms, preferably provide the each circulation of each encapsulating housing to be less than the positive particle and the negative ion source of 100 atoms.Preferably, can add positive particle and the negative ion source that capacity kation and cloudy particle source provide about 50 atoms of the each circulation of each encapsulating housing.These low concentrations can obtain by the solution of serial dilution cation and negative ion source.Metal ion source can be the slaine that comprises magnetic nano-particle, for example the Tetrachloroplatinate ammonium.Replaceable but not preferred, metal ion source can be present in the composition that wherein adds the organic macromolecule source.
The potpourri that can stir organic macromolecule and metallic ion is to guarantee uniformity coefficient.When magnetic nano-particle will comprise metal element or alloy, reduction took place on composition, and nano-sized metal particles is formed in the organic macromolecule hole.This reduction is preferably carried out with the protection metal nanoparticle not oxidized under inert atmosphere, and wherein the oxidation meeting reduces their magnetic.The reducing/oxidizing step can repeat progressively to form nano particle between metallic ion additive (can be identical or different in each cycle).
Reaction mixture can form being lower than under the temperature of preferred temperature, and described preferred temperature is the temperature that can form magnetic nano-particle, and this temperature then raises.Replacedly, metal ion source is added wherein encapsulating material source can remain at least 24 ℃ temperature, and metal ion source is added wherein.
Before losing its ternary structural, protein can tolerate the temperature up to 70 ℃ usually.Thereby at encapsulating material is in the embodiment of protein, and temperature of reaction can be up to about 70 ℃.For these embodiments, temperature of reaction preferably remains on more than 25 ℃, for example is higher than about 35 ℃.Temperature preferably keeps below about 60 ℃, for example is lower than about 50 ℃.
Be used for the encapsulation magnetic nano particle period of the day from 11 p.m. to 1 a.m of the present invention in preparation, hydration medium remains in the alkaline pH scope when forming magnetic core core nano particle in the macromolecular template.Described pH preferably remains on the scope of 7.5-8.5.This can realize by using buffer solution.Difference according to used encapsulants is used suitable solution.
Behind the preparation nano particle, before the stromal surface deposition, they are placed in the carrier fluid.If prepare nano particle in suspending liquid, suspending liquid can be the composition that constitutes carrier fluid or all so.Replacedly, nano particle can be from extracting in the suspending liquid of preparation and suspension again carrier fluid.The physical property of this fluid can be adjusted according to concrete application.For example encapsulate under the situation of nano particle at protein, environmental baseline, for example temperature, pH and ionic strength can maintain proper level, to avoid before deposition the unnecessary destruction of protein.
Also can adjust the character of carrier fluid so that drop is easy to deposit to stromal surface.For example, but the surface tension that can adjust carrier fluid to obtain higher spreadability.That carrier fluid can be hydration or non-hydrated, and have the additional additives of adjusting its physical property.In preferred embodiment, carrier fluid is a water.
In one embodiment, when the present invention relates to by ink jet printing method the inorganic nano-particle deposition of macromolecular material encapsulation, inorganic nano-particle is semiconductor particle preferably.
The third aspect of the present invention highly preferred embodiment provides a kind of method for preparing the semi-conductor nano particles film, and wherein said particle comprises by CdS, CdSe, CdTe, ZnS, ZnSe or the ZnTe of apoferritin or DPS encapsulation.
In some embodiments of the present invention first, second or the third aspect, after nano particle is deposited on the matrix, can remove the remaining inorganic particulate that does not have coating of encapsulating housing.
In other embodiments of the present invention, can handle encapsulating material, the remaining residue that encases nuclear core nano particle for example makes the charing of big molecule housing, for example about 300 ℃ high temperature by matrix is placed under the high temperature.Replacedly, if desired, can use laser pyrolysis processes original position charing nano particle.The pyrolysis nanoparticulate thin films is flammable burns big molecule housing by for example being higher than at high temperature under about 500 ℃ temperature.This preferably realizes by the inertia that controls environment, for example by introduce hydrogen or nitrogen in pyrolysis container.
Also can use other method to remove deproteinize encapsulating material, for example enzymatic degradation method or pH degeneration methods.Especially, protein can utilize beyond protease digestion or the pH scope by the pH value of composition being adjusted to protein stabilization and sex change for example is lower than about pH4.0 or is higher than about pH9.0.Then by for example cleaning matrix or being placed on the protein material of removing sex change in the air-flow.In preferred embodiment, be adjusted to by pH value and be lower than about pH4.0 and make protein denaturation composition.
The smooth film for preparing nano particle by ink jet printing method can strengthen by the liquid particle suspension of pre-service, to increase the monodispersity of particle.In addition, pre-service can be by removing the formation of undesirable fragment reinforcing membrane.Term " monodispersity " is meant that the variation of single magnetic nano-particle size in the present composition is less.Measure with regard to maximum nanoscale yardstick, this change usually should less than about 20%, preferably less than about 10% with most preferably less than about 5%.For the composition of the relatively large for example about 50nm of average-size, advantageous variant is at the lower limit of above-mentioned scope, and for less relatively particle, for example about 10nm, variation can be in the upper limit of above-mentioned scope.The size of particle of the present invention for example can use transmission electron microscope (TEM) method to measure.Examine the core nano particle by aspect big molecule or the encapsulation of protein housing in the present invention, before measuring nuclear core nano-particles size, be necessary to remove the housing in the encapsulation nano particle representative sample.This can use any method well known by persons skilled in the art to realize, any method by describing in detail above for example is as pyrolysismethod.
We have found to encapsulate the monodispersity of nano particle can be by carrying out micro-pore-film filtration to the fluid composition that comprises described nano particle before the deposition on the matrix, and deposition wherein is by for example ink jet printing method.In addition, this preparation process helps to remove undesirable fragment usually.
In preparatory filtration step, to the composition of encapsulation nano particle, although also can use in some embodiments other solvent for example alcohol or alkane be preferably hydration solution, carry out micro-pore-film filtration.In this filtration step, composition is guided to the one side of filtrator, and pass through membrane filtration.Be used for nano particle of the present invention and preferably be present in composition with the concentration of the about 20mg/mL of about 0.1-.In one embodiment, the pH of composition is preferably about 7-about 8.5.Preferably, in filtration step, composition is applied normal pressure.For example, exerting pressure can be greater than about 1psi, for example greater than about 5psi.Usually, pressure is less than about 20psi, for example less than about 15psi.Reclaim the filtrate that comprises nanoparticle compositions then.
Film filter is a known structure, and the difference of itself and non-film filter is that film is an one-piece construction, that is, solid-state structure forever is connected to form continuous solid phase.Comparatively speaking, non-film filter is to be formed by the fiber that is fixed on the appropriate location by mechanical interlocking or other surface force.If desired, the film filter of preparation can have narrow pore size distribution and very little hole.The about 10 μ m of the about 0.02-of hole dimension that are used for micropore filtering film of the present invention are preferably less than about 1 μ m with most preferably less than about 0.5 μ m; The object lesson that can be used for hole dimension of the present invention is the hole of about 0.2 μ m and the hole of about 0.1 μ m.Being used for the millipore filter that classification is ready to use in particle of the present invention can comprise polymkeric substance, metal, pottery, glass and carbon by multiple material preparation.Described film is usually by the known polymeric material preparation in described field, to be used in the membrane filtration, for example, polysulfones, polyethersulfone (PES), polyacrylate, polyvinylene base class (polyvinylidenes) are as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, cellulose esters or its multipolymer.Preferably when encapsulating material was protein, the film of selection comprised the material of low-protein associativity, for example polyethersulfone or polyvinylene.This class millipore filter can (Bedford MA) obtains from MilliporeCorporation.
Film filter can be the film disk, although the film filter of other form also is applicable to the present invention.
Importantly, we have found in order to prepare the stabilized nano particle composition, the big several magnitude of size of the comparable nanometer particle material of the order of magnitude of filter hole size.For example, when being used for particle of the present invention and being encapsulated by ferritin, the diameter of this protein is about 12nm.We find to use the filtrator of 0.2 μ m and 0.1 μ m can obtain to prevent that the ferritin of assembling from encapsulating the stable product of nano particle.
Usually, the size that is used for nano particle of the present invention usually at least about 1nm and be not more than about 100nm, preferably is not more than about 50nm and more preferably no more than about 20nm all in nano-scale range.Preferred magnetic of the present invention or semi-conductor nano particles are that diameter is the spheroid of about 1-100nm basically.But the present invention also extends to has the not magnetic particle in the nanoscale scope of one dimension size.
The present invention relates to the magnetic nano particle period of the day from 11 p.m. to 1 a.m, the pre-service purifying step can comprise the magnetic classification step that encapsulates magnetic nano-particle.This is included under the action of gravity or makes the fluid composition that contains magnetic nano-particle by the retardance medium by applying normal pressure and simultaneously it being applied magnetic field, thereby the particle in the composition spatially obtains separating according to their magnetic.No matter packed still not packed, because the magnetic of magnetic particle is by the size decision of nuclear core magnetic nano-particle, so this method also provides the nuclear core particle that obtains wherein to have the device of the composition of high single dispersion degree.
The retardance medium can comprise the steel part of other shape that Powdered, pearl or described field are known, for example IV 20L type or other suitable soft magnetic material.Although magnetic nano-particle can have the interactional form of inducing by stage equipment the time, preferably block medium comprise not with the magnetic nano-particle composition to destroy or to change the material of the mode generation chemical reaction of its structure.
Those skilled in the art can understand the plurality of devices that can obtain being used for the magnetic classification, for example magnetic line, Magnaglo chromatograph and field flow classification technique.In the preferred embodiment of the present invention, composition is about 0.2-10ml/min with the flow velocity -1Flow velocity by comprising the post of Magnaglo.The magnetic classification also has the advantage that nano particle suspension fluid media (medium) wherein can be exchanged.
At particle is under the situation of magnetic particle, and pretreatment stage can comprise filtration step or magnetic classification step, or comprises two steps of any order.
Embodiment by following indefiniteness sets forth the present invention:
Embodiment
The preparation apoferritin is as the description among the WO 98/22942.
Embodiment 1, synthesizes the cobalt/nano platinum particle in apoferritin
Apoferritin is dispersed in 0.05M 4-(2-hydroxyethyl)-1-piperazine ethane-sulfonic acid (HEPES) damping fluid is buffered to pH 7.5-8.5, or be dispersed among the 0.25M AMPSO and be buffered to pH7.5-8.5.Add cobalt (II) acetate solution of equivalent 0.1M and Tetrachloroplatinate (II) ammonium salt solution of 0.1M then, and when 35 ℃-50 ℃ of temperature, stir the mixture.Use sodium borohydride reduction then.Add a large amount of slaines, and reduce subsequently to obtain apoferritin, its center core is occupied (Mayes E 2002.J.Magn.Soc.Japan.26 (8) 932-935:Warne B et.Al.2000 IEE Transactions on Magnetics 363009-3011) basically by the Co/Pt crystal.
Embodiment 2. synthesizes the iron-nano platinum particle in apoferritin
Apoferritin is dispersed in 50mM 3-([1,1-dimethyl-2-hydroxyethyl] amino)-2-hydroxypropanesulfonic acid (AMPSO) solution, and is buffered to pH 8.5-8.9; Suspension temperature is maintained 40 ℃-70 ℃.The ammonium sulfate iron (II) that adds equivalent in apoferritin suspending liquid gradually (25mM) and Tetrachloroplatinate ammonium (II) de gassed solution (25mM).The iron (II) that adds and equivalent part of platinum (II) are equivalent to 100 atoms in each apoferritin molecule.After each time adds iron, add the Trimethylamine-N-oxide (25mM) of the iron (II) of the stoichiometry equivalent that is equivalent to iron (II) 2/3.Treat that each time adds platinum (II) afterwards, adds stoichiometric suitable reductive agent, for example sodium borohydride or hydrazine.The time interval that adds gradually between equivalent part is about 15 minutes, and during except adding iron (II) oxide, it is to add immediately add iron (II) in reaction suspension after.Add to proceed to and filled up by magnetic iron ore/platinum (O) nuclear core basically until apoferritin.Water is dialysed to suspending liquid then, and the filtrator by 0.2 μ m filters before concentrating or preparing use.
Embodiment 3. with the ferritin ink jet printing on glass matrix
With many boxs of Oliver Design (SN252) disk cleaning systems cleaning glass substrate.
Use EPSON ink-jet printer (image 1290) in the following process: use syringe that the ferritin water slurry that protein concentration is about 2-10mg/ml is introduced printing head, wherein printing head has-the static head of 5cm (about 0.075psi).
Disk is placed in the disk fixing casket, and is placed on the fixed position of injection head below.Ferritin suspending liquid is with at 10-100cm sec -1Between a variation speed deposit on the glass disk.
In some cases, use identical ferritin material disk to be carried out the ink jet printing in another cycle.
After the ferritin deposition, remove disk and also analyze with atomic force microscope (AFM).Find that this painting method obtains the film that thickness is 100nm-12nm, the latter is the feature of ferritin individual layer.The AFM collection of illustrative plates of sample as shown in Figure 5.
Cobalt-platinum ink jet printing that embodiment 4 will be encapsulated by apoferritin is on glass matrix
With many boxs of Oliver Design (SN252) disk cleaning systems cleaning glass substrate.
In following process, use EPSON ink-jet printer (image 1290): use syringe that the water slurry (it can contain the hydrazine up to 0.2%) that protein concentration is about the described cobalt-platinum alloy that is encapsulated by apoferritin of the embodiment 1 of 2-10mg/ml is introduced printing head, printing head wherein has-the static head of 5em (about 0.075psi).
Disk is placed in the disk fixing casket, and is placed on the fixed position of injection head below.The composition of the metal alloy that is encapsulated by apoferritin is with at 10-100cm sec -1Between a variation speed be deposited on the glass disk.
In some cases, use the identical cobalt-alloy platinum material that is encapsulated by apoferritin disk to be carried out the ink jet printing in another cycle.
Embodiment 5 with the ferritin ink jet printing to on the pretreated glass matrix of ultraviolet ray
With many boxs of Oliver Design (SN252) disk cleaning systems cleaning glass substrate.
Before ink jet printing under the nitrogen atmosphere matrix being placed under the ultraviolet source (wavelength 172nm) (USHIO).Especially, matrix is placed in apart from the position of putting into the about 2mm of quartz glass of UV filament, and under the UV line, places about 20-40 second.
In following process, use EPSON ink-jet printer (photo 1290): use syringe that the ferritin water slurry (it can contain the hydrazine up to 0.2%) that protein concentration is about 2-10mg/ml is introduced printing head, printing head wherein has-the static head of 5cm (about 0.075psi).
Disk is placed in the disk fixing casket, and is placed on the fixed position of injection head below.Ferritin suspending liquid is with at 10-100cm sec -1Between a variation speed be deposited on the glass disk.
In some cases, use identical ferritin material disk to be carried out the ink jet printing in another cycle.
The AFM collection of illustrative plates of sample is not as shown in Figure 6 behind irradiation and the UV-irradiation.
Iron-platinum ink jet printing that embodiment 6 will be encapsulated by apoferritin is to on the pretreated matrix of UV light
With many boxs of Oliver Design (SN252) disk cleaning systems cleaning glass substrate.
Before ink jet printing under the nitrogen atmosphere matrix being placed under the ultraviolet light source (wavelength 172nm) (USHIO).Especially, matrix is placed in apart from the position of putting into the about 2mm of quartz glass of UV filament, and under the UV line, places about 20-40 second.
In following process, use EPSON ink-jet printer (image 1290): use syringe that the water slurry (it can contain the hydrazine up to 0.2%) that protein concentration is about the iron/platinum alloy that is encapsulated by apoferritin of 2-10mg/ml such as embodiment 2 is introduced printing head, printing head wherein has-the static head of 5cm (about 0.075psi).
Disk is placed in the disk fixing casket, and is placed on the fixed position of injection head below.The composition of the metal alloy that is encapsulated by apoferritin is with at 10-100cm sec -1Between a variation speed deposit on the glass disk.
In some cases, use the identical cobalt-alloy platinum material that is encapsulated by apoferritin disk to be carried out the ink jet printing in another cycle.
Cobalt-platinum ink jet printing that embodiment 7 will be encapsulated by apoferritin is to on the pretreated glass matrix of UV light
With many boxs of Oliver Design (SN252) disk cleaning systems cleaning glass substrate.
Before ink jet printing under the nitrogen atmosphere matrix being placed under the ultraviolet light source (wavelength 172nm) (USHIO).Especially, matrix is placed in apart from the position of putting into the about 2mm of quartz glass of UV filament, and under the UV line, places about 20-40 second.
In following process, use EPSON ink-jet printer (image 1290): use syringe that the water slurry (it can contain the hydrazine up to 0.2%) that protein concentration is about the cobalt/platinum alloy that is encapsulated by apoferritin of 2-10mg/ml such as embodiment 1 is introduced printing head, printing head wherein has-the static head of 5cm (about 0.075psi).
Disk is placed in the disk fixing casket, and is placed on the fixed position of injection head below.The composition that is encapsulated by apoferritin is with at 10-100cm sec -1Between a variation speed be deposited on the glass disk.
In some cases, use the identical cobalt-alloy platinum material that is encapsulated by apoferritin disk to be carried out the ink jet printing in another cycle.

Claims (86)

1. a formation has the method for the magnetic recording system of magnetisable film of nanoparticles, it comprises the suspending liquid of the magnetisable nano particle of preparation in carrier fluid, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, form the described film of magnetisable nano particle as the dry residue of deposits fluid suspending liquid.
2. method as claimed in claim 1 wherein deposits to described fluid suspension on the matrix by ink jet printing method.
3. as the method for claim 1 or 2, wherein said magnetic nano-particle is formed on to small part in the big molecule housing.
4. method as claimed in claim 3, wherein said big molecule housing is a protein.
5. method as claimed in claim 4, wherein said protein are apoferritin or DPS.
6. as each method among the claim 3-5, wherein subsequently by film of nanoparticles being placed the high temperature more than 300 ℃ make the carbonization of described big molecule housing.
7. as each method among the claim 3-5, wherein subsequently by the pyrolysis film of nanoparticles burns described big molecule housing under 500 ℃ the temperature being higher than.
8. the method for each claim as described above, the average surface roughness R of wherein said matrix aLess than about 1nm.
9. as each method among the claim 1-7, the average surface roughness R of wherein said matrix aBe the about 20nm of about 5nm-.
10. the method for each claim is as described above wherein handled dispersion with the nanoparticle suspension that promotes to apply to described matrix.
11. as the method for claim 10, wherein said processing comprises chemistry, machinery or radiation treatment.
12. as the method for claim 11, wherein said radiation treatment comprises matrix is placed under the ultraviolet light.
13. the method for each claim wherein deposits to nano particle on the matrix and afterwards film is handled as described above.
14., wherein after depositing to nano particle on the matrix, film is annealed as the method for claim 13.
15. the method for each claim as described above, the thickness of wherein said film is not more than 2 diameters (comprising any encapsulating housing) that spread all over the particle of whole film basically.
16. the method for each claim as described above, wherein film is lip-deep discontinuous in height less than about 13nm.
17. the method for each claim as described above, the diameter of wherein said magnetic nano-particle when nonspherical particle (or maximum gauge) is not more than 20nm.
18. the method for each claim as described above, wherein said magnetic nano-particle comprises the alloy of cobalt and platinum.
19. the method for each claim as described above, wherein said magnetic nano-particle is packed.
20. as the method for claim 19, wherein said encapsulating material is a protein.
21. as the method for claim 20, wherein said protein is apoferritin or DPS.
22. as each method among the claim 19-21, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
23. as the method for claim 22, the hole dimension of wherein said film filter is 0.02-10 μ m.
24. as the method for claim 22 or 23, wherein said film comprises polyethersulfone or polyvinylene (polyvinylidene).
25. the method for each claim is wherein being carried out the magnetic classification to described magnetic nano-particle before the deposition on the matrix as described above.
26. method for preparing magnetisable film, it comprises the suspending liquid of the magnetisable nano particle of preparation in carrier fluid, wherein said each magnetisable nano particle is formed on to small part in the protein housing, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described magnetisable film as the dry residue of deposits fluid suspending liquid.
27., wherein described fluid suspension is deposited on the matrix by ink jet printing method as the method for claim 26.
28. as the method for claim 26 or 27, wherein subsequently by matrix being placed the high temperature more than 300 ℃ make the charing of described protein housing.
29., wherein burn described big molecule housing being higher than pyrolysis film of nanoparticles under about 500 ℃ temperature subsequently as the method for claim 26 or 27.
30. as each method among the claim 26-29, the average surface roughness R of wherein said matrix aLess than about 1nm.
31. as each method among the claim 26-29, the average surface roughness R of wherein said matrix aBe the about 20nm of about 5nm-.
32., wherein described matrix is handled dispersion with the nanoparticle suspension that promotes to apply as each method among the claim 26-31.
33. as the method for claim 32, wherein said processing comprises chemistry, machinery or radiation treatment.
34. as the method for claim 33, wherein said radiation treatment comprises matrix is placed under the ultraviolet light.
35. as each method among the claim 26-34, wherein nano particle deposits the back described film is handled on matrix.
36. as the method for claim 35, wherein nano particle is deposited on the matrix and after the deposition film is annealed.
37. as each method among the claim 26-36, the variation in thickness of wherein said film is not more than about 3 diameters (comprising any encapsulating housing) that spread all over the component particle of whole film substantially.
38. as each method among the claim 26-37, the average surface roughness R of wherein said film aBe not more than the diameter (comprising any encapsulating housing) of about 3 particles.
39. as each method among the claim 26-38, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
40. as each method among the claim 26-39, the diameter of wherein said magnetic nano-particle when nonspherical particle (or maximum gauge) is not more than 20nm.
41. as each method among the claim 26-40, wherein said magnetic nano-particle comprises the alloy of cobalt and platinum.
42. as each method among the claim 26-41, wherein said encapsulating material is a protein.
43. as the method for claim 42, wherein said protein is apoferritin or DPS.
44. as each method among the claim 26-43, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
45. as the method for claim 44, the hole dimension of wherein said film filter is 0.02-10 μ m.
46. as the method for claim 44 or 45, wherein said film comprises polyethersulfone or polyvinylene.
47., wherein before the deposition magnetic nano-particle is being carried out the magnetic classification on the matrix as each method among the claim 26-46.
48. method that on matrix, forms the inorganic nano-particle film, it comprises the suspending liquid of preparation inorganic nano-particle in carrier fluid, wherein each inorganic nano-particle is formed on to small part in the protein housing, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described film as the dry residue of deposits fluid suspending liquid.
49., wherein described fluid suspension is deposited on the matrix by ink jet printing method as the method for claim 48.
50. as the method for claim 48 or 49, wherein subsequently by matrix being placed the high temperature more than 300 ℃ make the charing of described protein housing.
51. as the method for claim 48 or 49, wherein subsequently by the pyrolysis film of nanoparticles burns described big molecule housing under about 500 ℃ temperature being higher than.
52. as each method among the claim 48-51, the average surface roughness R of wherein said matrix aLess than about 1nm.
53. as each method among the claim 48-51, the average surface roughness R of wherein said matrix aBe the about 20nm of about 5nm-.
54., wherein described matrix is handled to promote the dispersion of coated nanoparticles suspending liquid as each method among the claim 48-53.
55. as the method for claim 54, wherein said processing comprises chemistry, machinery or radiation treatment.
56. as the method for claim 55, wherein said radiation treatment comprises matrix is placed under the ultraviolet light.
57. as each method among the claim 48-56, wherein nano particle is handled film after depositing on matrix.
58. as the method for claim 57, wherein nano particle is annealed to film after depositing on matrix.
59. as each method among the claim 48-58, the variation of wherein said film thickness is not more than the diameter (comprising any encapsulating housing) of about 3 component particles on the degree of depth.
60. as each method among the claim 48-59, the average surface roughness R of wherein said film aBe not more than the diameter (comprising any encapsulating housing) of about 3 particles.
61. as each method among the claim 48-60, wherein said inorganic nano-particle comprises magnetic material or semiconductor material.
62. as the method for claim 61, wherein said inorganic nano-particle comprises semiconductor material.
63. as the method for claim 62, wherein said inorganic nano-particle is a semi-conductor nano particles, comprises by CdS, CdSe, CdTe, ZnS, ZnSe or the ZnTe of apoferritin or DPS encapsulation.
64. as each method among the claim 48-63, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
65. as each method among the claim 48-64, the diameter of wherein said magnetic nano-particle when nonspherical particle (or maximum gauge) is not more than 20nm.
66. as each method among the claim 48-65, wherein said protein housing comprises apoferritin or DPS.
67. as each method among the claim 48-66, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
68. as the method for claim 67, the hole dimension of wherein said film filter is 0.02-10 μ m.
69. as the method for claim 67 or 68, wherein said film comprises polyethersulfone or polyvinylene.
70. method that forms protein film in stromal surface, the thickness of wherein said protein film is less than about 10 times of the diameter of component protein plasmid that spreads all over whole film substantially, it comprises the suspending liquid of preparation protein granule in carrier fluid, described protein granule is carried out membrane filtration, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, on matrix, obtain described film as the dry residue of deposits fluid suspending liquid.
71., wherein described fluid suspension is deposited on the matrix by ink jet printing method as the method for claim 70.
72. as the method for claim 70 or 71, the surfaceness R of wherein said matrix aLess than about 1nm.
73. as the method for claim 70 or 71, the surfaceness R of wherein said matrix aBe the about 20nm of about 5nm-.
74., wherein described matrix is handled to promote the dispersion of coated nanoparticles suspending liquid as each method among the claim 70-73.
75. as the method for claim 74, wherein said processing comprises chemistry, machinery or radiation treatment.
76. as the method for claim 75, wherein said irradiation treatment comprises matrix is placed under the ultraviolet light.
77. as each method among the claim 70-76, wherein protein granule is handled film after depositing on matrix.
78., wherein after the protein granule deposition, film is annealed as each method among the claim 70-77.
79. as each method among the claim 70-78, the variation of wherein said film thickness is not more than about 3 diameters (comprising any encapsulating housing) that spread all over the component particle of whole film substantially on the degree of depth.
80. as each method among the claim 70-79, the surfaceness R of wherein said film aBe not more than about 3 particle diameters.
81. as each method among the claim 70-80, wherein said protein is apoferritin or DPS.
82. as each method among the claim 70-81, wherein the composition to the encapsulation nano particle carries out micro-pore-film filtration before deposition on the matrix.
83. as the method for claim 82, the hole dimension of wherein said film filter is 0.02-10 μ m.
84. as the method for claim 82 or 83, wherein said film comprises polyethersulfone or polyvinylene.
85. magnetic recording system with magnetisable film of nanoparticles, wherein said nano particle has been prepared in the suspending liquid of carrier fluid, and described fluid suspension deposited to stromal surface with volume less than the droplet form of about 1nL, form the described film of magnetisable nano particle as the dry residue of deposits fluid suspending liquid.
86., wherein described nano particle is deposited on the described matrix by ink jet printing method as the magnetic recording system of claim 85.
CN 200480007446 2003-03-18 2004-03-11 Production of nanoparticulate thin films Pending CN1762000A (en)

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