CN109179311B - A kind of method and preparation method thereof detecting column self-assembled film structure - Google Patents
A kind of method and preparation method thereof detecting column self-assembled film structure Download PDFInfo
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Abstract
The invention discloses it is a kind of detect column self-assembled film structure method, comprising: respectively construct materials A and with substrate most stable of interfacial structure a and material B and with the most stable of interfacial structure b of substrate；Calculate separately the interface bonding energy (E of interfacial structure afA) and interfacial structure b interface bonding energy (EfB)；Calculate interface bonding energy (EfA) and interface bonding energy (EfB) difference, if the difference be greater than zero, materials A is formed as nano-pillar and is embedded in material B；If the difference, less than zero, material B is formed as nano-pillar and is embedded in materials A.The structure for being formed by vertical column self-assembled film can be predefined using the method for the vertical column self-assembled film structure of judgement provided in an embodiment of the present invention, vertical column self-assembled film can selectively be prepared, it saves and prepares material, improve preparation efficiency.
Description
Technical field
The present invention relates to films and device preparation technical field, more particularly, to a kind of detection column self-assembled film structure
Method and preparation method thereof.
Background technique
With the fast development of electronic device, the miniaturization of device and the multi-functional hair for becoming next-generation electronic equipment
Open up direction.In order to realize the miniaturization of device, while exploitation obtains more new capabilities, and scientists are by multiple physical attribute collection
It is largely explored at into a system and to it.Wherein, many Scientific Research Workers find the heterogeneous outer of vertical self assembly
Prolong nanostructure: nanometer column material being embedded in the matrix of another material, infusive is that this structure shows often
Interesting performance out, such as magnetoelectric effect (ME Effect), magnetoresistance (MR Effect) and photoelectricity electrochemistry
Performance etc..Based on this, the hetero-epitaxy nanostructure of vertical shape self assembly is highly studied.But at present at this
In field, there are no any methods can predict that materials A and material B are formed by vertical shape self-assembled film, which material
Material will form nano-pillar.
Summary of the invention
The object of the present invention is to provide a kind of methods and preparation method thereof for detecting column self-assembled film structure, pass through structure
Construction material A and with substrate most stable of interfacial structure a and material B and with the most stable of interfacial structure b of substrate；Calculate interface
Interface bonding energy (the E of structure afA) and interfacial structure b interface bonding energy (EfB)；According to interface bonding energy (EfA) and interface
In conjunction with energy (EfB) size determine A material and B material is any is formed as vertical nano-pillar, it is any to be formed as substrate, can
Accurate detection is formed by the structure of columnar thin-film.Technical staff can determine that the film of the structure is according to above-mentioned calculated result
Be not it is required, if it is technical staff largely prepares it, can be with if it is not, there is no need to be prepared
Avoid many experiments；Meanwhile technical staff can also save according to the material structure of the interface bonding energy design of material
Material is saved while time.
To solve the above problems, the first aspect of the present invention provides a kind of side for detecting right cylinder shape self-assembled film structure
Method, comprising: using the method for first principle construct respectively materials A and with substrate most stable of interfacial structure a and material B
With with the most stable of interfacial structure b of substrate；Calculate separately the interface bonding energy (E of interfacial structure afA) and interfacial structure b boundary
Face combines can (EfB)；Calculate interface bonding energy (EfA) and interface bonding energy (EfB) difference, if the difference be greater than zero, by
Materials A and material B are formed by the structure of column self-assembled film, and materials A is nanometer column material, and material B is basis material；
If the difference less than zero, is formed by the structure of column self-assembled film by materials A and material B, material B is nano-pillar material
Material, materials A is basis material.
Further, interface bonding energy (EfA) calculating step include: to be calculated separately using the method for first principle: A
Gross energy E when most stable after film and the complete relaxation of substrate that material is formedAThe film that (film/substrate), A material are formed is complete
Gross energy E when complete freeAGross energy E (substrate) when (film), substrate are completely free；Interface bonding energy is calculated according to formula
(EfA), wherein formula are as follows: interface bonding energy (EfA)=[EA(film/substrate)-EA(film)-E (substrate)]/interfacial area.
Further, interface bonding energy (EfB) calculating step include: to be calculated separately using the method for first principle: B
Gross energy E when most stable after film and the complete relaxation of substrate that material is formedBThe film that (film/substrate), B material are formed is complete
Gross energy E when complete freeBGross energy E (substrate) when (film), substrate are completely free；Interface bonding energy is calculated according to formula
(EfA), wherein formula are as follows: interface bonding energy (EfA)=[EA(film/substrate)-EA(film)-E (substrate)]/interfacial area.
Further, the condition of the method for first principle are as follows: sewed using projection plus wave pseudo potential PAW, electron exchange are associated with
Generalized gradient approximation GGA and plane wave truncation in functional PBE can be 450eV；Wherein, it usesModified tetrahedron
The total data that method obtains first principle optimizes processing, and the value of K point is 3 × 3 × 1 in optimization process.
Further, A material, B material and substrate are mono-crystalline structures；Preferably, A material and/or B material are more iron materials
Material；A material and/or B material are ferromagnetic material.
The another aspect of this law invention, provides a kind of method for preparing column self-assembled film, comprising: uses above-mentioned side
The structure of film to be prepared is calculated and determined in method；Double target alternating growth systems are deposited using pulse laser to connect nanometer column material
After continuous strike m times, n times are continuously hit to basis material, m times of strike and n times constitute a strike circulation；Repeatedly recycled
Strike, control each circulate on substrate a unit cell height for being formed by thickness while being less than A material and B material.
Further, before continuously being hit m times using the double target alternating growth systems of pulse laser deposition nanometer column material,
Further include: use impulse laser deposition system in grown on substrates a layer thickness for the epitaxial oxide hearth electrode of 10~50nm.
Above-mentioned technical proposal of the invention has following beneficial technical effect:
(1) it can be predefined using the method for the vertical column self-assembled film structure of judgement provided in an embodiment of the present invention
It is formed by the structure of vertical column self-assembled film, vertical column self-assembled film can be selectively prepared, save
It prepares material, improve preparation efficiency.
(2) method for using first-principles calculations two interface bonding energies provides for the crystal structure of self-assembled film
Prediction and experiment instruction.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram for the detection column self-assembled film structure that an embodiment of the present invention provides；
Fig. 2 is two kinds of interfacial structure schematic diagrames of middle building according to a first embodiment of the present invention；
Fig. 3 is the method flow schematic diagram of middle preparation column self-assembled film according to a second embodiment of the present invention；
Fig. 4 is the structural schematic diagram of the column self-assembled film prepared according to second embodiment；
Fig. 5 is the schematic diagram for preparing extension object oxide hearth electrode according to second embodiment；
Fig. 6 is the apparatus structure schematic diagram for preparing vertical column self-assembled film according to a second embodiment of the present invention；
Fig. 7 is two kinds of interfacial structure schematic diagrames of middle building according to a third embodiment of the present invention；
Fig. 8 is the schematic diagram of two kinds of interfacial structures of middle building according to a fourth embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment and join
According to attached drawing, the present invention is described in more detail.It should be understood that these descriptions are merely illustrative, and it is not intended to limit this hair
Bright range.In addition, in the following description, descriptions of well-known structures and technologies are omitted, to avoid this is unnecessarily obscured
The concept of invention.
Fig. 1 is the method flow schematic diagram for the detection column self-assembled film structure that an embodiment of the present invention provides.
As shown in Figure 1, the method comprising the steps of S101- step S103；
Step S101, using the method for first principle construct respectively materials A and with the most stable of interfacial structure a of substrate,
And material B and with the most stable of interfacial structure b of substrate.
Interface constructed by A material, B material and baseplate material may have in very much, calculate separately A material, B material and base
A variety of interface bonding energies constructed by plate material, the conduct that selection interface combines energy minimum in a variety of interface bonding energies respectively is most
Stable interfacial structure a and most stable of interfacial structure b, then with most stable of interfacial structure a and most stable of interfacial structure b
For research object.
It should be noted that establish a mathematical model by computer, the mathematical model be about two kinds of materials and
Each atom, atom key and space structure in substrate etc. are the mathematical models how to show, by inputting on computers
The crystal structure and lattice of the crystal structure and lattice parameter of A material, the crystal structure of B material and lattice parameter and substrate ginseng
Number constructs the interfacial structure formed there may be materials A and baseplate material and structure by technical staff by operation computer
Build the interfacial structure that material B that may be present and baseplate material are formed.
Step S102 calculates separately the interface bonding energy (E of interfacial structure afA) and interfacial structure b interface bonding energy
(EfB)。
Specifically, interface bonding energy (EfA) calculating step include: to be calculated separately using the method for first principle: A material
Gross energy E when most stable after film and the complete relaxation of substrate that material is formedAThe film that (film/substrate), A material are formed is complete
Gross energy E when freeAGross energy E (substrate) when (film), substrate are completely free；Interface bonding energy is calculated according to formula
(EfA), wherein formula are as follows: interface bonding energy (EfA)=[EA(film/substrate)-EA(film)-E (substrate)]/interfacial area.
It should be noted that when multiple energy values above-mentioned using first-principles calculations, due to the lattice of materials A and substrate
Constant has slightly difference, so can have certain lattice mismatch phenomenon between materials A and substrate, and lattice mismatch phenomenon meeting
The film prepared is set to generate certain strain, so calculating EAIt, need to be by raising whole timber in film when (film/substrate)
The lattice parameter of A is expected so that A material and substrate are formed by strain is consistent with the strain that experimental result obtains.Adjust materials A
Lattice parameter when, can search bibliography can be obtained strain in corresponding experiment.Such as reference database model
In A material and the crystal structure mismatch of substrate be 1%, and the corresponding crystalline substance of corresponding strain is generated during actually growing
Lattice mismatch is 2%, so calculating EAWhen (film/substrate), the lattice parameter of A material is adjusted, so that lattice mismatch reaches
2%.
It should also be noted that, complete relaxation is the process for gradually returning to equilibrium state from some state.Here
Material and substrate are combined together by calculating when referring to initial, still, during calculating, computer can be automatically adjusted and be taken
The relative position of the atom key position built, the atom can slightly change, and the structure finally combined is no longer that technical staff passes through meter
The position that calculation machine is built, the state built from beginning technical staff enter the state of a relative equilibrium.Specifically, interface cohesion
It can (EfB) calculating step include: to be calculated separately using the method for first principle: B material formed film and substrate relax completely
Gross energy E when most stable behind HenanBGross energy E when the film that (film/substrate), B material are formed is completely freeB(film), base
Gross energy E (substrate) when plate is completely free；Interface bonding energy (E is calculated according to formulafB), wherein formula are as follows: interface bonding energy
(EfB=[EB(film/substrate)-EB(film)-E (substrate)]/interfacial area.
It should be noted that when multiple energy values above-mentioned using first-principles calculations, due to the lattice of material B and substrate
Constant has slightly difference, so can have certain lattice mismatch phenomenon between material B and substrate, and lattice mismatch phenomenon meeting
The film made is set to generate certain strain, so calculating EBIt, need to be by being raised in relaxation film when (film/substrate)
The lattice parameter of whole timber material B is so that B material and substrate are formed by strain is consistent with the strain that experimental result obtains.Adjust B
When the lattice parameter of material, can search bibliography can be obtained the strain in testing accordingly.Such as reference database
The crystal structure mismatch of B material and substrate in model is 1%, and is generated corresponding to corresponding strain during actually growing
Lattice mismatch be 2%, so calculate EBWhen (film/substrate), the lattice parameter of B material is adjusted, so that lattice mismatch reaches
To 2%.The condition of the above-mentioned method using first principle are as follows: sewed using projection plus wave pseudo potential PAW, electron exchange are associated with functional
PBE and plane wave truncation can be 450eV；Wherein, it usesModified tetrahedral method obtains first principle complete
Portion's data optimize processing, and the value of K point is 3 × 3 × 1 in optimization process.That is, in optimization process, X, Y, Z tri-
The number for having used K point on direction respectively is 3,3,1.
It should be noted that using plane wave base group to atomic nucleus outside electron wave function be unfolded when, due to interior
Layer electronics is bound at nuclear core, this just needs very big base group that could obtain preferable approximation.And usual substance
Chemical property be mainly by atomic nucleus outside valence electron influenced, inner electron and the electronics phase interaction outside other atomic nucleus
With weaker, the variation for causing inner electron outside atomic nucleus to influence chemical property is little.At this point, with an imaginary electrostatic
Gesture carrys out potential caused by the electronics at substitution atoms core, and this reduces the quantity of the electronics of required calculating and base groups
Size greatly reduces calculation amount, so that bigger counting system can be simulated by adopting this method.This imaginary electrostatic potential
Referred to as pseudo potential.
Truncation can be the plane wave that much energy are got after indicating plane wave expansion, shared after expansion for energetic portions
Ratio it is very small, and influence calculating speed, so be not truncation can be the bigger the better.Truncation can be the handle in calculating pseudo potential
The energy of valence state electronics and core (core state) electronics separated (cut off).The purpose of pseudo potential is exactly to obtain a gesture best to retouch
Its behavior to valence state electronics is stated, therefore valence state and core state how to be selected to have the influence of essence that valence is being determined pseudo potential behavior
After state and core state, the wave function that we need to select core area radius (truncation radius) core area electronics is truncated, that is, it is so-called
Match radii, this radius choose the behavior for directly affecting and generating pseudo potential.
On the basis of being built upon ideal uniform electronic gas model due to LDA, and the electronics of practical atom and molecular system
Density far from uniform, so usually chemistry often can not be met by the chemical property of the LDA atom being calculated or molecule
The requirement of family.Further increase computational accuracy, it is necessary to consider the heterogeneity of electron density, this is generally by exchanging
The gradient for introducing electron density in correlation energy functional is completed, i.e. generalized gradient approximation GGA.
Step S103 calculates interface bonding energy (EfA) and interface bonding energy (EfB) difference, if the difference be greater than zero,
Materials A is formed as nano-pillar and is embedded in material B；If the difference, less than zero, material B is formed as nano-pillar and is embedded in materials A
In.If the difference is equal to zero, self-assembled film can not be formed, will as one layer film or what is obtained is two kinds of materials
The thin film mixed.
That is, be formed by the structure of column self-assembled film if difference is greater than zero by materials A and material B,
Materials A is nanometer column material (Pillar), and material B is basis material (Matrix)；If difference is less than zero, by materials A and material B
It is formed by the structure of column self-assembled film, material B is nanometer column material, and materials A is basis material.
It should be noted that A material, B material and substrate are mono-crystalline structures, and A material and B material do not melt mutually, for example,
The atom framework structure of A material cannot form another atom framework structure with the atom framework structure of B material, it is assumed that the original of A
Minor structure is square, and the atomic structure of B is cuboid, and A and B not will form another irregular atomic structure, about not
The A material and B material mutually melted can be inquired by consulting literatures.Preferably, A material and/or B material are ferroelectric material or ferromagnetic material
Material.If A material, B material and substrate are not mono-crystalline structures, will be unable to prepare vertical column self-assembled film.
Above-mentioned technical proposal of the invention has following beneficial technical effect:
(1) institute's shape can be predefined using the method for detection column self-assembled film structure provided in an embodiment of the present invention
At vertical column self-assembled film structure, can selectively prepare column self-assembled film, saving prepares material, mentions
High preparation efficiency.
(2) first principle is used to calculate separately the method for the interface bonding energy of two materials as the crystal of self-assembled film
Structure provides prediction and experiment instruction.
The step of elaborating the above method below in conjunction with specific embodiments.
Embodiment one
Fig. 2 is two kinds of interfacial structure schematic diagrames of middle building according to a first embodiment of the present invention.
As shown in Fig. 2, the present embodiment selects multi-iron material bismuth ferrite BiFeO3With dielectric material cerium oxide CeO2For film
The strontium titanates SrTiO for preparing material, selecting (001) direction3Be discussed in detail as an example for substrate, but the present invention not with
This is limited.Due to bismuth ferrite BiFeO3With cerium oxide CeO2There is no electric conductivity, therefore can not directly carry out electrical testing, needs
In BiFeO3、CeO2Increase by one layer of epitaxial oxide hearth electrode between substrate.At this point, by epitaxial oxide hearth electrode directly with
BiFeO3And CeO2Contact, therefore, extension object hearth electrode is equivalent to a laminar substrate, when calculating interfacial structure, needs to calculate extension
Oxide hearth electrode and BiFeO3And CeO2Interfacial structure.The present embodiment epitaxial oxide hearth electrode is with ruthenic acid strontium SrRuO3For
Example.
Left side is bismuth ferrite BiFeO3With ruthenic acid strontium SrRuO3Most stable of interfacial structure schematic diagram, right side is titanium dioxide
Cerium CeO2With ruthenic acid strontium SrRuO3Most stable of interfacial structure schematic diagram.
Above two interface bonding energy is calculated separately, wherein bismuth ferrite BiFeO3With ruthenic acid strontium SrRuO3Interface cohesion
It can be -1.81J/m2, ceria CeO2With ruthenic acid strontium SrRuO3Interface bonding energy be -3.33J/m2。
Bismuth ferrite BiFeO3With ruthenic acid strontium SrRuO3Interface bonding energy and ceria CeO2With substrate ruthenic acid strontium SrRuO3
Interface bonding energy difference be 1.52 > 0.Therefore, bismuth ferrite BiFeO3, ceria CeO2With ruthenic acid strontium SrRuO3What is constituted is perpendicular
In right cylinder shape self-assembled film, bismuth ferrite BiFeO3It will form vertical column and be embedded in ceria CeO2In.
Embodiment two
Fig. 3 is the method flow schematic diagram of middle preparation column self-assembled film according to a second embodiment of the present invention.
As shown in figure 3, this method comprises: step S201- step S203.
The present embodiment selects multi-iron material bismuth ferrite BiFeO3With dielectric material cerium oxide CeO2For film prepare material,
Select the strontium titanates SrTiO in (001) direction3It is discussed in detail as an example for substrate, due to bismuth ferrite BiFeO3And cerium oxide
CeO2There is no electric conductivity, therefore can not directly carry out electrical testing, needs in BiFeO3、CeO2Increase by one layer between substrate
Epitaxial oxide hearth electrode.At this point, directly and BiFeO by epitaxial oxide hearth electrode3And CeO2Therefore contact is calculating interface
When structure, need to calculate epitaxial oxide hearth electrode and BiFeO3And CeO2Interfacial structure.Epitaxial oxide bottom in the present embodiment
Electrode is with ruthenic acid strontium SrRuO3For.
It should be noted that it is able to carry out electrical testing if the vertical column self-assembled film generated is conductive,
It can not need to prepare one layer of extension object hearth electrode on substrate.
Firstly, it is necessary to using impulse laser deposition system in substrate (001) SrTiO3Upper growth a layer thickness be 10~
50nm extension object hearth electrode ruthenic acid strontium SrRuO3.Extension object hearth electrode ruthenic acid strontium SrRuO3Growth conditions are as follows: frequency 10Hz, swash
Light energy is 300mJ, and the distance of target to substrate is 40mm, and oxygen pressure is 70~150mTorr, and temperature is 650~720 DEG C, growth
Time is 20 minutes.
Preferably, oxygen pressure is 100mTorr, and temperature is 690 DEG C, with a thickness of 20nm.If oxygen presses oxygen pressure too low, can make
Its anoxic, makes crystal structure change.Oxygen pressure is too high, then can make ruthenic acid strontium SrRuO3Surface texture become coarse and raw
Length slows.Temperature is too low, then not exclusively, temperature is excessively high, then can destroy ruthenic acid strontium SrRuO for crystallization3Crystal structure, and wave
Take resource.Thickness is too low, then electric conductivity is bad, and thickness is excessively high, waste of resource.
Step S201 deposits double target alternating growth systems using pulse laser and continuously hits m times nanometer column material, then
N times are continuously hit to basis material, m times of strike and n times constitute a circulation strike.
Specifically, to nanometer column material bismuth ferrite BiFeO3Continuous strike m times, then to basis material ceria CeO2
Continuous strike n times, m times of strike and the one circulation strike of n times composition.
Step S202 repeatedly carries out circulation strike, in ruthenic acid strontium SrRuO3Growth has the film of preset thickness on layer,
In, it is controlled during circulation strike and each circulates in ruthenic acid strontium SrRuO3On be formed by thickness while being less than bismuth ferrite BiFeO3
With ceria CeO2A unit cell height.
It should be noted that influence of the thickness of single cycle strike for film is most important, if thickness is blocked up
Vertical columnar film is not will form.Therefore single cycle strike is formed by a unit cell of the thickness no more than two kinds of materials
Highly.
Specifically, target bismuth ferrite BiFeO3With target ceria CeO2Distance to substrate is 40mm；Frequency is
10Hz；Laser energy is that the temperature of 300mTorr circulation strike is 600-700 DEG C, preferably 650 DEG C；Oxygen pressure is 70-
150mTorr, preferably oxygen press 100mTorr；The proportional region of n and m are as follows: 5:75-5:300, preferably 5:200.
If the temperature of circulation strike is lower than 600 DEG C, two kinds of materials cannot crystallize well；If recycling the temperature of strike
Degree is higher than 700 DEG C of then BiFeO3Bi volatilization in the vertical column self-assembled film formed, the structure and ferroelectric properties meeting of crystal
It is very poor.
It should also be noted that, when the proportional region of n and m is more than 5:75-5:300, two kinds of materials in made film
Structure it is not clear enough.
Step S203 is continually fed into a large amount of oxygen, and the cooling rate for controlling film is no more than 0.4 DEG C/s, until film is cold
But to room temperature.
Specifically, after the completion of film growth, it need to be passed through a large amount of oxygen rapidly, oxygenating processing is carried out to film, while is right
Film carries out cooling processing, until film cools to room temperature (30 DEG C or so).Controlling the oxygen pressure around film is 300mTorr, drop
Warm speed is no more than 0.4 DEG C/s.It is passed through a large amount of oxygen rapidly, oxygenating processing is carried out to film primarily to reducing in film
Lacking oxygen, thus reduce film electric leakage, improve the ferroelectric properties of film.
It should be noted that, if the excessive velocities of cooling, can generate and answer in the crystal of film after the completion of film growth
Power has an impact to the structure of film, therefore the speed to cool down is no more than 0.4 DEG C/s.
By vertical columnar thin-film prepared by the above method, ferroelectric memory field can be applied to, due to ferroelectric material
Ceria CeO is embedded in as nano-pillar2In, increasing considerably for ferroelectric memory storage density may be implemented.
Fig. 4 is the structural schematic diagram of the column self-assembled film prepared according to second embodiment.
As shown in figure 4, the forming process of vertical column self-assembled film are as follows: deposit double target alternating growths by pulse laser
System is to bismuth ferrite BiFeO3(BFO is referred to as in figure) and ceria CeO2It alternately hits, so that in extension object hearth electrode ruthenic acid
Strontium SrRuO3One layer of BFO-CeO is formed on (being referred to as SRO in figure)2Vertical column self-assembled film, bismuth ferrite in the film
BiFeO3It will form vertical nano-pillar and be embedded in ceria CeO2In.
Fig. 5 is the schematic diagram for preparing extension object oxide hearth electrode according to second embodiment.
As shown in figure 5, control impulse laser deposition system, beats laser beam in ruthenic acid strontium SrRuO3(referred to as SRO) target
On the surface of material, the ruthenic acid strontium SrRuO of laser facula is touched3Target material surface ablated steaming because of the high density energy of laser
It sends out, the target particle, drop under high temperature encounter ruthenium of the laser of high energy to form central bright similar to flame again in the sky
Sour strontium SrRuO3Plumage brightness, substrate (001) SrTiO being deposited under the action of adding laser outside immediately below plumage brightness3On.
Fig. 6 is the apparatus structure schematic diagram for preparing vertical column self-assembled film according to a second embodiment of the present invention.
As shown in fig. 6, control pulse laser deposits double target systems, beat laser beam in bismuth ferrite BiFeO3Under target n, make
A part of bismuth ferrite BiFeO3It is grown in ruthenic acid strontium SrRuO3On；Rotary target material exchanger, makes laser beam beat CeO2Target m times makes
A part of CeO2It is grown in ruthenic acid strontium SrRuO3On.It repeats to hit repeatedly, in the surface ruthenic acid strontium SrRuO of extension object hearth electrode3On
Form one layer of vertical column self-assembled film.
The BFO-CeO that the device for preparing vertical column self-assembled film provided through the embodiment of the present invention obtains2Vertically
Column self-assembled film can be applied in ferroelectric memory, using the nano-pillar in self-assembled nano structures as ferroelectric material,
Increasing considerably for storage density may be implemented.The ferroelectricity that the hetero-epitaxy nanostructure of this vertical self assembly simultaneously is formed is received
Meter Zhu Ke avoids the latent lesion of photo-etching process directly as function element.
Embodiment three
Fig. 7 is two kinds of interfacial structure schematic diagrames of middle building according to a third embodiment of the present invention.
As shown in fig. 7, present embodiment selects multi-iron material bismuth ferrite BiFeO3With ferromagnetic material cobalt ferrite CoFe2O4For
The strontium titanates SrTiO for preparing material, selecting (001) direction of film3It is discussed in detail as an example for substrate, but the present invention
It is not limited thereto.Due to bismuth ferrite BiFeO3With cobalt ferrite CoFe2O4There is no electric conductivity, therefore can not directly carry out electricity
Test, needs in BiFeO3、CoFe2O4Increase by one layer of epitaxial oxide hearth electrode between substrate.At this point, by epitaxial oxide
Hearth electrode is directly and BiFeO3And CoFe2O4Contact, therefore, extension object hearth electrode is equivalent to a laminar substrate, is calculating interfacial structure
When, need to calculate epitaxial oxide hearth electrode and BiFeO3And CoFe2O4Interfacial structure.The present embodiment epitaxial oxide bottom electricity
Pole is with ruthenic acid strontium SrRuO3For.
Right side is bismuth ferrite BiFeO3(abbreviation BFO) and ruthenic acid strontium SrRuO3The most stable of interfacial structure of (abbreviation SRO) is shown
It is intended to, left side is cobalt ferrite CoFe2O4(abbreviation CFO) and ruthenic acid strontium SrRuO3Most stable of interfacial structure schematic diagram.
Above two interface bonding energy is calculated separately, wherein bismuth ferrite BiFeO3With ruthenic acid strontium SrRuO3Interface cohesion
It can be -1.81J/m2, cobalt ferrite CoFe2O4With ruthenic acid strontium SrRuO3Interface bonding energy be -1.02J/m2。
Cobalt ferrite CoFe2O4/ ruthenic acid strontium SrRuO3Interface bonding energy and bismuth ferrite BiFeO3/ ruthenic acid strontium SrRuO3Interface
It is 0.79 > 0 in conjunction with energy difference.Therefore, available conclusion: bismuth ferrite BiFeO3, cobalt ferrite CoFe2O4With ruthenic acid strontium (001)
SrRuO3In the vertical column self-assembled film that substrate is constituted, cobalt ferrite CoFe2O4It will form vertical column and be embedded in bismuth ferrite
BiFeO3In.
About above-mentioned cobalt ferrite CoFe2O4With bismuth ferrite BiFeO3It is formed by cobalt ferrite CoFe2O4For nanometer column material, iron
Sour bismuth BiFeO3For basis material, ruthenic acid strontium (001) SrRuO3For the preparation of the vertical column self-assembled film of extension object hearth electrode
Method, it is identical as the mode of the preparation method of above-described embodiment two, therefore do not repeating.
This vertical column prepared by the method for embodiment three is from group leader's membrane structure, with individual cobalt ferrite
CoFe2O4Or individual bismuth ferrite BiFeO3The two kinds of films formed are compared, and ferromagnetic property can be obviously improved.
Example IV
The present embodiment four is with multi-iron material bismuth ferrite BiFeO3With ferromagnetic material cobalt ferrite CoFe2O4Material is prepared for film
Material, the strontium titanates SrTiO for selecting (111) direction3It is discussed in detail as an example for substrate due to bismuth ferrite BiFeO3With
CoFe2O4There is no electric conductivity, therefore can not directly carry out electrical testing, needs in BiFeO3、CoFe2O4Increase between substrate
One layer of epitaxial oxide hearth electrode.At this point, directly and BiFeO by epitaxial oxide hearth electrode3And CoFe2O4Contact, therefore, outside
Prolong object hearth electrode and be equivalent to a laminar substrate, when calculating interfacial structure, needs to calculate epitaxial oxide hearth electrode and BiFeO3With
CoFe2O4Interfacial structure.The present embodiment epitaxial oxide hearth electrode is with ruthenic acid strontium (111) SrRuO3For.
Left side is bismuth ferrite (111) BiFeO3With ruthenic acid strontium (111) SrRuO3Most stable of interfacial structure schematic diagram, it is right
Side is cobalt ferrite (111) CoFe2O4With ruthenic acid strontium (111) SrRuO3Most stable of interfacial structure schematic diagram.
Above two interface bonding energy is calculated separately, wherein bismuth ferrite (111) BiFeO3With ruthenic acid strontium (111) SrRuO3
Interface bonding energy be -1.59J/m2, cobalt ferrite (111) CoFe2O4With ruthenic acid strontium (111) SrRuO3Interface bonding energy be-
4.38J/m2。
Bismuth ferrite (111) BiFeO3/ ruthenic acid strontium (111) SrRuO3Interface bonding energy and cobalt ferrite (111) CoFe2O4/ ruthenium
Sour strontium (111) SrRuO3Interface bonding energy difference be 2.79 > 0.Therefore, bismuth ferrite BiFeO3, cobalt ferrite CoFe2O4With ruthenic acid
Strontium (111) SrRuO3In the vertical column self-assembled film that substrate is constituted, cobalt ferrite CoFe2O4It will form vertical column and be embedded in iron
Sour bismuth BiFeO3In.
About above-mentioned cobalt ferrite CoFe2O4With bismuth ferrite BiFeO3It is formed by cobalt ferrite CoFe2O4For nanometer column material, iron
Sour bismuth BiFeO3For basis material, ruthenic acid strontium (111) SrRuO3For the preparation of the vertical column self-assembled film of extension object hearth electrode
Method, it is identical as the mode of the preparation method of above-described embodiment two, therefore do not repeating.
The BFO- that the device of vertical column self-assembled film prepared by four methods provided obtains through the embodiment of the present invention
The vertical column self-assembled film of CFO can obtain magnetoelectric effect (ME Effect), with individual cobalt ferrite CoFe2O4Or
Individual bismuth ferrite BiFeO3The two kinds of films formed are compared, and can be obviously improved ferromagnetic property, be can be applied to electronic device
In.
It should be noted that embodiment three and example IV are all the strontium titanates SrTiO by selecting different directions3As
Substrate will lead to entirely different interface bonding energy, so that identical two kinds of substances are grown on the substrate of different directions, be formed
Vertical column self-assembled structures be it is completely different, further demonstrate by using detection column provided in an embodiment of the present invention
The method of shape self-assembled film structure can predefine the structure for being formed by vertical column self-assembled film, can there is selection
Property preparation column self-assembled film, saving prepares material, improves preparation efficiency.
It should be understood that above-mentioned specific embodiment of the invention is used only for exemplary illustration or explains of the invention
Principle, but not to limit the present invention.Therefore, that is done without departing from the spirit and scope of the present invention is any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.In addition, appended claims purport of the present invention
Covering the whole variations fallen into attached claim scope and boundary or this range and the equivalent form on boundary and is repairing
Change example.
Claims (7)
1. a kind of method for detecting column self-assembled film structure characterized by comprising
Using the method for first principle construct respectively materials A and with substrate most stable of interfacial structure a and material B and with
The most stable of interfacial structure b of substrate；
Calculate separately the first interface bonding energy (E of the interfacial structure afA) and interfacial structure b second contact surface combination energy
(EfB)；
Calculate the first interface bonding energy (EfA) can (E in conjunction with the second contact surfacefB) difference, if the difference is greater than
Zero, then it is formed by the structure of column self-assembled film by materials A and material B, materials A is nanometer column material, and material B is base
Body material；If the difference less than zero, is formed by the structure of column self-assembled film by materials A and material B, material B is
Nanometer column material, materials A is basis material.
2. the method according to claim 1, wherein the first interface bonding energy (EfA) calculating step packet
It includes:
It is calculated separately using the method for first principle: total when most stable after film and the complete relaxation of substrate that materials A is formed
ENERGY EAGross energy E when the film that (film/substrate), materials A are formed is completely freeAIt is total when (film), substrate are completely free
ENERGY E (substrate)；
The first interface bonding energy (E is calculated according to formulafA), wherein formula are as follows: the first interface bonding energy (EfA)=[EAIt is (thin
Film/substrate)-EA(film)-E (substrate)]/interfacial area.
3. the method according to claim 1, wherein the second contact surface combines energy (EfB) calculating step packet
It includes:
It is calculated separately using the method for first principle: total when most stable after film and the complete relaxation of substrate that material B is formed
ENERGY EBGross energy E when the film that (film/substrate), material B are formed is completely freeBIt is total when (film), substrate are completely free
ENERGY E (substrate)；
Second contact surface, which is calculated, according to formula combines energy (EfB), wherein formula are as follows: second contact surface combines can (EfB)=[EB(film/
Substrate)-EB(film)-E (substrate)]/interfacial area.
4. according to the method in claim 2 or 3, which is characterized in that the condition of the method for the first principle are as follows: use
Projection is sewed and adds wave (PAW) pseudo potential, described exchange correlation letter and plane wave truncation using the PBE in generalized gradient approximation (GGA)
It can be 450eV.
5. the method according to claim 1, wherein the materials A, material B and substrate are mono-crystalline structures.
6. a kind of method for preparing column self-assembled film characterized by comprising
Using the structure of the described in any item method detection self-assembled films of claim 1-5, determine that materials A is nano-pillar material
Material, material B are basis material；
After continuously being hit m times using the double target alternating growth systems of pulse laser deposition the nanometer column material, to described matrix
Material continuously hits n times, and m times of strike and n times constitute a circulation strike；
Circulation strike repeatedly is carried out, has the film of preset thickness in grown on substrates；Wherein, it is controlled during circulation strike each
A unit cell height for being formed by thickness while being less than the nanometer column material and described matrix material is circulated on substrate；
A large amount of oxygen are continually fed into, the cooling rate for controlling the film is no more than 0.4 DEG C/s, until the film cooling to room
Temperature.
7. according to the method described in claim 6, it is characterized in that, depositing double target alternating growth systems to institute using pulse laser
It states before a nanometer column material continuously hits m times, further includes:
The epitaxial oxide hearth electrode for using impulse laser deposition system to grow a layer thickness on the substrate for 10~50nm.
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| CN101748489A (en) * | 2009-10-16 | 2010-06-23 | 齐齐哈尔大学 | Method for self-assembling Bi4-xYxTi3O12 ferroelectric film at low temperature |
| CN102011190A (en) * | 2010-12-22 | 2011-04-13 | 南京工业大学 | Method for preparing nanostructure barium strontium titanate ferroelectric film by utilizing nanocrystalline self assembly process |
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| CN101748489A (en) * | 2009-10-16 | 2010-06-23 | 齐齐哈尔大学 | Method for self-assembling Bi4-xYxTi3O12 ferroelectric film at low temperature |
| CN102011190A (en) * | 2010-12-22 | 2011-04-13 | 南京工业大学 | Method for preparing nanostructure barium strontium titanate ferroelectric film by utilizing nanocrystalline self assembly process |
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