CN107785166A - A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy - Google Patents

A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy Download PDF

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CN107785166A
CN107785166A CN201711091911.XA CN201711091911A CN107785166A CN 107785166 A CN107785166 A CN 107785166A CN 201711091911 A CN201711091911 A CN 201711091911A CN 107785166 A CN107785166 A CN 107785166A
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magnetic alloy
dilute magnetic
uniaxial anisotropy
lft
concentration
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CN107785166B (en
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白飞明
代书洋
张怀武
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University of Electronic Science and Technology of China
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    • 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
    • H01F41/24—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 from liquids
    • H01F41/26—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 from liquids using electric currents, e.g. electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

Abstract

A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy, including：First, adhesion layer and Seed Layer are sputtered successively on a silicon substrate；Then negative electrode is used as using the substrate with adhesion layer and Seed Layer, conducting metal block is as anode, under conditions of 600~1000Oe magnetic field is applied to the direction parallel to substrate surface, electrochemical deposition is carried out using three-electrode method, deposition voltage is 1.1~1.5V, sedimentation time is 100~400s, obtains dilute magnetic alloy.The dilute magnetic alloy that the inventive method obtains has excellent high-frequency soft magnetic performance and uniaxial anisotropy, its negative magnetoconductivity appears in more than 1GHz, and there is reduction crystallite dimension, surface roughness and coercitive effect simultaneously, it can meet that multilayer film interconnection line, transmission line and waveguide are to the magnetospheric demand of negative magnetoconductivity in integrated device.

Description

A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy
Technical field
The present invention relates to a kind of preparation method of dilute magnetic alloy with uniaxial anisotropy, available for multilayer film interconnection Negative magnetoconductivity layer in line, or need in low-coercivity, higher cutoff frequency, the inductance of high magnetic permeability and magnetic core of transformer film, In the integrated device and integrated device transmission line that need excellent soft magnet performance.
Background technology
At present, magnetic device, such as inductance, transformer, high frequency noise suppressor, magnetic head, Magnetic Sensor, with human being's production It is closely bound up with living.Current electronics just progressively move towards integrated and high frequency, and the miniaturization of magnetic device and high frequency Change relatively lags behind.Snoek laws show that in the case where the saturation magnetization of magnetic material is certain, cut-off frequency is higher, has Effect magnetic conductivity is lower, and vice versa.This just seriously limits magnetic device and developed to high frequency.In order to break through Snoek laws Limitation, it can be introduced while from the magnetic material with high saturation and magnetic intensity in membrane-film preparation process suitable single Axle anisotropy field so that film meets the Acher limit, i.e.,：
Wherein, μiFor initial permeability, frNatural resonant frequency is represented, γ represents gyromagnetic ratio, and 4 π Ms are that saturated magnetization is strong Degree, HkRepresent uniaxial anisotropy field.Obviously, the magnetic conductivity of thin magnetic film with uniaxial anisotropy and multiplying for cut-off frequency Product not only with 4 π MsSize it is related, and with 4 π Ms/HkIt is related.By adjusting 4 π Ms/Hk, can be in 1~5GHz frequency applications In the range of obtain more than 200 magnetic conductivity.In the case of less demanding to magnetic conductivity, it might even be possible to by the application of thin magnetic film Frequency is expanded to more than 10GHz.
Except the demand of high frequency, have also appeared in recent years to the demand with high frequency, negative magnetoconductivity thin magnetic film.Example Such as, in integrated circuit interconnection line application, traditional copper, aluminum interconnecting can cause alternating current due to the presence of eddy current effect Skewness so that for electric current close to the surface of conductor and as conductor gradually successively decreases, this will result in interconnection line Overall electrical resistance and loss increase.At present, common improved method be using the smaller gold of resistivity as interconnection line, but its into This is higher, is not suitable for large-scale production and prepares.In addition, reducing the thickness of interconnection line, it is less than skin depth, also can Realizing reduces the effect of eddy-current loss, but this method can increase D.C. resistance and ohmic loss.Chinese patent ZL201410415806.7 propose it is a kind of by dilute magnetic alloy MCu (M=Fe, Ni, Co, Mn etc.) films and Cu layers (non-magnetic material, Magnetic conductivity is 1) to be alternatively formed multi-layer film structure, obtained be approximately zero Effective permeability, in theory can be by skin depth Infinity is brought up to, so as to significantly reduce eddy-current loss；Moreover, the thickness of the multilayer film can regulate and control, can reduce simultaneously D.C. resistance and ohmic loss.However, this method is not directed to the uniaxial anisotropy of dilute magnetic thin film, and uniaxial anisotropy is The key of high applying frequency and negative magnetoconductivity is obtained, this is due to that isotropism MCu alloy firms have the magnetic moment being orientated in a jumble And multidomain structure, its effective damping factor are larger, it is difficult to obtain resonance type magnetic spectrum, namely can not obtain effective negative magnetoconductivity.
It can be seen that uniaxial anisotropy thin magnetic film not only passes to film transformer, thin film inductor, noise suppressor, magnetic field The frequency applications of the devices such as sensor, high density magnetic record magnetic head have positive impetus, but also can be extended to interconnection line In the emerging application such as winding coil.But at present, the preparation of uniaxial anisotropy thin magnetic film is often using sputtering or vacuum Evaporation, not only equipment is complicated, and it is higher to prepare cost.
The content of the invention
A kind of the defects of present invention exists for background technology, it is proposed that system of the dilute magnetic alloy with uniaxial anisotropy Preparation Method.The dilute magnetic alloy that the inventive method obtains has excellent high-frequency soft magnetic performance and uniaxial anisotropy, its negative magnetic conductance Rate appears in more than 1GHz, and has simultaneously and reduce crystallite dimension, surface roughness and coercitive effect, can meet inductance, Transformer, magnetic head and Magnetic Sensor are to the demand with excellent high frequency soft magnet performance and the magnetic core film of uniaxial anisotropy.
Technical scheme is as follows：
A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy, specifically includes following steps：
Step 1, sputter adhesion layer and Seed Layer successively on a silicon substrate；
Step 2, dilute magnetic alloy formed in the Seed Layer that step 1 obtains using electrochemical deposition method：Obtained with step 1 Substrate with adhesion layer and Seed Layer is applied as negative electrode, conducting metal block as anode to the direction parallel to substrate surface Under conditions of the magnetic field for adding 600~1000Oe, electrochemical deposition is carried out using three-electrode method, deposition voltage is -1.1~-1.5V, Sedimentation time is 100~400s, obtains dilute magnetic alloy；Wherein, the plating solution of electrochemical deposition is CuSO4, soluble metallic salt, lemon Lemon acid sodium, the mixed aqueous solution of brightener.
Further, adhesion layer described in step 1 is the thick Ti layers of 30~50nm, and Seed Layer is the thick Cu layers of 80~100nm. Ti layers can effectively improve adhesive force of the conductive layer in substrate, while stop the based diffusion of Cu layers so that Seed Layer is more Uniformly；The lattice constant of Cu Seed Layers and the lattice match of dilute magnetic alloy are high, will not produce considerable influence to stress.
Further, to being rectangle by being positioned over beside electrochemical deposition groove parallel to the magnetic field that substrate surface applies What magnet was realized, the rectangular magnet is placed parallel to substrate surface.
Further, in the plating solution of electrochemical deposition described in step 2, CuSO4Concentration be 0.02mol/L；Soluble gold Category salt is one kind in soluble cobalt, soluble nickel salt, soluble ferric iron salt, and its concentration is 0.125~0.5mol/L；Citric acid The concentration of sodium is 0.02~0.046mol/L；Brightener is the LFT- that Guangzhou Li Fante is surface-treated Science and Technology Ltd.'s production 930Mu, LFT-930A and LFT-930B, wherein, LFT-930Mu concentration is 8mL/L, and LFT-930A concentration is 0.5mL/L, LFT-930B concentration is 0.5mL/L；
Further, sedimentation time described in step 2 is 100~200s.
Further, contacted described in step 2 as between the substrate and electrode of negative electrode for face.As shown in Fig. 2 it is electrochemistry The method of clamping schematic diagram of substrate during deposition；Wherein, two elastic copper sheets are fixed on T-shape fixture, the two elastic copper sheets lead to The mode for crossing face contact contacts with one side of substrate, while copper sheet will not produce magnetic field for the magnetic field that applies in substrate and do Disturb, ensure that the magnetic field's regularity in substrate, be advantageous to induce anisotropy.Compared to the mode of single-point clamping, the face The bilateral method of clamping of contact can significantly improve the uniformity of the dilute magnetic alloy film of electrochemical deposition, and this is due in single-point During clamping, the magnitude of voltage of central point is maximum, and ring-type pressure drop is presented by circle of central point, and the bilateral method of clamping of the present invention is then big The big inhomogeneities for reducing Potential distribution.
Present invention also offers the dilute magnetic alloy film that a kind of above method obtains integrated device interconnection line, transmission line and Application in waveguide.
Beneficial effects of the present invention are：
The present invention carries out electrochemical deposition using single groove, passes through contact the silicon chip with adhesion layer and Seed Layer with face Mode is connected with electrode is used as negative electrode, is applied by the rectangular magnet being positioned over beside electroplating bath on parallel to silicon chip direction External magnetic field forms dilute magnetic alloy on a silicon substrate with induced anisotropic using the method for electrochemical deposition.The inventive method Obtained dilute magnetic alloy has excellent high-frequency soft magnetic performance and uniaxial anisotropy, and its negative magnetoconductivity appears in more than 1GHz, And its grain size and coercivity have also obtained effective control, inductance, transformer, magnetic head and Magnetic Sensor can be met to excellent The demand of the magnetic core film of good high-frequency soft magnetic performance and uniaxial anisotropy.
Brief description of the drawings
Fig. 1 is the schematic device that electrochemical deposition process of the present invention uses；Wherein, 1 is electrochemical deposition groove, and 2 be square Shape magnet, 3 be T-shape fixture, and 4 be anode material；
The method of clamping schematic diagram of substrate when Fig. 2 is electrochemical deposition of the present invention；
Fig. 3 is the XRD spectrum for the CoCu alloy firms that the embodiment of the present invention obtains under different sedimentation potentials；
Fig. 4 is the hysteresis curve for the CoCu alloy firms that the embodiment of the present invention obtains under different sedimentation potentials；
Fig. 5 is the magnetic spectrum test curve figure for the CoCu alloy firms that the embodiment of the present invention obtains under different sedimentation potentials；
Fig. 6 be in the obtained CoCu alloy firms of the inventive method anisotropy with the change schematic diagram of thickness；Wherein, scheme (a), (b), (c), (d) correspond to hysteresis curve of the sedimentation time for the obtained film of 100s, 200s, 300s, 400s respectively；
Fig. 7 is surface of the sodium citrate to film that various concentrations are added in the CoCu alloy firms that the inventive method obtains The influence of roughness and grain size；
Fig. 8 is coercive of the sodium citrate to film that various concentrations are added in the CoCu alloy firms that the inventive method obtains The influence of power.
Embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail.
Embodiment
A kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy, specifically includes following steps：
Step 1, common silicon chip is chosen as substrate, be successively H in volume ratio2SO4：H2O2=1：1 mixed liquor, go from It is cleaned by ultrasonic in sub- water, acetone, absolute ethyl alcohol, nitrogen drying；
Ti adhesion layers and Cu Seed Layers are sputtered successively in step 2, the silicon chip after step 1 cleaning：After step 1 is cleaned Silicon chip is put into magnetron sputtering apparatus, fixed Ti targets and Cu targets, is evacuated to 10-4Below Pa；Then, air valve is opened, is being sputtered Under conditions of air pressure is 0.6Pa, sputtering power is 80W, the thick Ti adhesion layers of 35nm are formed using the method for radio-frequency sputtering；Upper Walk and the thick Cu Seed Layers of 100nm are formed using the method for radio-frequency sputtering on the Ti adhesion layers formed, sputtering pressure 0.5Pa, splash It is 65W to penetrate power；After the completion of sputtering, radio-frequency power supply and sputtering equipment are closed, you can Ti adhesion layers and Cu kinds are formed on silicon chip Sublayer；
Step 3, by CoSO4·7H2O、CuSO4·5H2O, sodium citrate, LFT-930Mu, LFT-930A and LFT-930B Add in 1.5L deionized water, plating solution of the obtained mixed solution as electrochemical deposition；Wherein, in the mixed solution CoSO4·7H2O concentration is 0.125mol/L, CuSO4·5H2O concentration is 0.02mol/L, and the concentration of sodium citrate is 0.0453mol/L, LFT-930Mu concentration are 8mL/L, and LFT-930A concentration is 0.5mL/L, and LFT-930B concentration is 0.5mL/L；
Step 4, the seed obtained in electroplating bath as shown in Figure 1 using electrochemical deposition method after step 2 processing CoCu dilute magnetic alloys are formed on layer：Step 3 is prepared to obtained mixed solution to be transferred in electroplating bath as shown in Figure 1, will be walked The silicon chip obtained after rapid 2 processing, which is held on by the way of as shown in Figure 2 on copper sheet, is used as negative electrode, makes shape between silicon chip and electrode Contacted into face, copper billet is positioned over by electroplating bath as anode, calomel electrode as reference electrode, rectangular magnet parallel to silicon chip Side, to realize to the electromagnetic field for applying 800Oe sizes parallel to silicon chip surface direction, it is dilute that CoCu is formed using electrochemical deposition method Magnetic alloy, deposition voltage are -1.1V, sedimentation time 200s；
After step 5, electrochemical deposition terminate, silicon chip is taken out, is dried up using deionized water rinsing, and with nitrogen, you can To the CoCu dilute magnetic alloys with uniaxial anisotropy；
Further, in MCu dilute magnetic alloys of the present invention, on the one hand, Cu addition can improve M=Ni, Fe, Co soft magnetism Performance, on the other hand, by taking CoCu as an example, CoCu alloys and Cu Seed Layers are all face-centred cubic structures, can effectively reduce magnetosphere With stress problem caused by non-magnetosphere lattice mismatch, be advantageous to the dilute magnetic alloy film that resistivity is small, tack is good.
Further, when forming dilute magnetic alloy using electrochemical deposition method in step 4, the silicon chip as negative electrode uses Fig. 2 The shown face way of contact contacts with electrode, greatly reduces the inhomogeneities of Potential distribution so that the film of deposition is more equal It is even；External magnetic field is applied on parallel to substrate surface direction by the rectangular magnet being positioned over beside electroplating bath, it is good to induce Good anisotropy.
As shown in figure 1, it is the structural representation of the electroplating bath used in electrochemical deposition process of the present invention；Wherein, 1 is electricity Chemical sedimentation groove, using the electroplating bath that volume is 1.5L in embodiment；2 be rectangular magnet, is positioned over electroplating bath both sides, phase It can on a silicon substrate be produced away from 10cm, in embodiment and be oriented parallel to substrate, the uniformity magnetic that size is 800Oe；3 be " T " Type fixture, for clamping and fixing silicon chip；4 be anode material.
As shown in Fig. 2 for electrochemical deposition of the present invention when silicon chip method of clamping schematic diagram；Wherein, on T-shape fixture Two elastic copper sheets are fixed, the two elastic copper sheets contact by way of face contacts with one side of silicon chip, while copper sheet pair Magnetic interference will not be produced in the magnetic field applied on substrate, ensure that the magnetic field's regularity on substrate, is advantageous to induce Anisotropy.Compared to the mode of single-point clamping, the bilateral method of clamping of face contact can significantly improve electrochemical deposition The uniformity of dilute magnetic alloy film, this is due to when single-point clamps, and the magnitude of voltage of central point is maximum, is in by circle of central point Existing ring-type pressure drop, and the bilateral method of clamping of the present invention then greatly reduces the inhomogeneities of Potential distribution.
In the case that the negative potential on negative electrode is in overpotential, the Cu on anode2+It can precipitate into solution, and and plating M ions (M=Ni, Fe, Co) in liquid are co-deposited on cathode substrate.Under normal circumstances, within the specific limits, negative electrode is negative Current potential is higher, and the nucleus of formation is smaller, and magnetocrystalline anisotropy energy is smaller, and the uniaxial anisotropy of formation is better.It is however, excessive Negative potential can cause M in alloy firm (M=Ni, Fe, Co) increase again, for example, as M=Co, if Co in alloy firm Content more than 80%, can cause original centroid cubic lattice structure to close-packed hexagonal structure change, cause interfacial stress Increase；Therefore, the uniaxial anisotropy for choosing dilute magnetic alloy film of the suitable deposition voltage to obtaining has important influence.
The properties of the CoCu alloy firms to being obtained under different sedimentation potentials, which are analyzed, below further illustrates：
Deposition voltage in embodiment is changed into -1.3V, -1.5V, remaining operating procedure is constant, obtains in not synsedimentary electricity XRD spectrum, hysteresis curve and the magnetic spectrum test curve of CoCu alloy firms under position (- 1.1V, -1.3V, -1.5V) are respectively such as Shown in Fig. 3,4 and 5.
Fig. 3 is the XRD spectrum of the CoCu alloy firms obtained under different sedimentation potentials；From the figure 3, it may be seen that with deposition electricity The increase of position, the peak value in (111) face of CoCu alloys, which has, substantially moves to right trend, shows what is obtained in the case that sedimentation potential is more negative Co contents are more in CoCu films.Copper is face-centred cubic structure, and Co is close-packed hexagonal structure, and test result shows in deposition electricity Press the lattice constant closest to copper for the alloy firm obtained during -1.1V；And in the case where voltage is excessively negative, there is solid matter six The diffraction maximum of square structure, show that CoCu alloys are gradually transitions close-packed hexagonal structure by face-centred cubic structure, and be formed at silicon substrate Cu Seed Layers on piece are face-centred cubic structure, and this, which may result in, produces larger stress between alloy firm and Cu Seed Layers, It is unfavorable for the attachment of alloy firm, it is easy to fall off.Therefore, suitable deposition voltage is kept to the obtained component of alloy firm and attached Put forth effort to have a great impact.
Fig. 4 is the hysteresis curve of the CoCu alloy firms obtained under different sedimentation potentials；As shown in Figure 4, with deposition The increase of current potential, the increase of its coercivity, while uniaxial anisotropy reduces.When sedimentation potential reaches -1.6V, apply outside magnetic Field is all difficult to induce the CoCu films with uniaxial anisotropy, and because film deposition rate is too fast, its thickness occurs Serious inhomogeneities.As can be seen here, suitable deposition voltage to the uniaxial anisotropy performance of obtained alloy firm with And uniformity has great influence.
Fig. 5 is the magnetic spectrum test curve of the CoCu alloy firms obtained under different sedimentation potentials；As shown in Figure 5 ,- There is negative magnetoconductivity in the CoCu alloy firms obtained under 1.1V, -1.3V, -1.5V sedimentation potentials, still, with deposition voltage Rise, the direction that its cut-off frequency reduces to frequency moves, and limits the frequency of use of the film, -1.1V sedimentation potential The cut-off frequency of device can be improved, is more beneficial for its application in high-frequency element.As can be seen here, suitable deposition voltage is to obtaining To the applying frequency of alloy firm have important influence.
In addition, the thickness of obtained dilute magnetic alloy film also has vital influence to its uniaxial anisotropy.When When the dilute magnetic alloy film arrived is excessively thin, Cu Seed Layers can have interdiffusion phenomenon with MCu alloy-layers, influence its soft magnet performance；When When obtained dilute magnetic alloy film is blocked up, because MCu alloys have higher magnetic conductivity in itself, Kelvin effect can be produced.Below Performance evaluation to the CoCu alloy firms of different-thickness (i.e. different sedimentation times) further illustrates：Will be heavy in embodiment Product the time be changed into 100s, 300s, 400s, remaining operating procedure is constant, obtain different sedimentation times (100s, 200s, 300s, The hysteresis curve of the CoCu alloy firms of the different-thickness obtained under 400s) is as shown in Figure 6；Wherein, deposition 100s is obtained thin Film thickness is 153nm (a), and the film thickness that deposition 200s is obtained is 236.3nm (b), and the film thickness that deposition 300s is obtained is 336nm (c), the film thickness that deposition 400s is obtained is 398nm (d).It will be appreciated from fig. 6 that when film thickness is more than 150nm, it is thin Film starts uniaxial anisotropy occur；When film thickness reaches 236nm, its magnetic conductivity is 198, and anisotropy field is 46.5Oe.The hysteresis curve of easy axle shows in Fig. 6, when deposited between when being 200s, the soft magnet performance of obtained film is excellent, its Area of hysteresis loop is smaller, and magnetic conductivity is high, and remanent magnetism is small, shows typical elongate, while its film thickness is relatively thin (236.3nm), uniformity is also guaranteed.
Generally, boric acid can be added in the plating solution of electrochemical deposition to adjust its pH value, however, adding the acid of plating solution after boric acid Property reduce, aggravated reaction in hydrogen evolution phenomenon so that film surface stomata increase, uniformity reduce.And the present invention does not have Its acidity is adjusted using boric acid, but by adding sodium citrate, while control the content of sodium citrate to regulate and control the pH value of plating solution For 2.8~3.1, be advantageous to obtain the dilute magnetic alloy film with uniaxial anisotropy, while change roughness of film Kind effect is also very notable.
Further, in retaining surface on the premise of uniaxial anisotropy, the size and surface roughness of MCu crystal grain can shadows Coercivity is rung, and excessive coercivity can cause high frequency magnetic loss and the reduction of magnetic conductivity, be unfavorable for the dilute magnetic alloy film Application in high frequency.The performance evaluation of the CoCu alloy firms obtained below under the sodium citrate to adding various concentrations enters one Walk explanation：By the concentration of the sodium citrate added in embodiment be changed into 0mol/L, 0.0114mol/L, 0.0227mol/L, 0.034mol/L, remaining operating procedure is constant, obtains in addition various concentrations (0mol/L, 0.0114mol/L, 0.0227mol/ L, 0.034mol/L, 0.0453mol/L) sodium citrate under the obtained surface roughness of CoCu alloy firms and crystal grain it is big Small, coercitive result difference is as shown in FIG. 7 and 8.The sodium citrate of addition can be with the Co in plating solution2+And Cu2+Form complexity Complex compound so that cathodic reduction current potential reduces the reduction process completed to ion, and so, the speed of growth of nucleus is less than forming core speed Degree, cause generation crystal grain it is smaller, film surface is more smooth；Meanwhile the sodium citrate of addition can also cause electroplate liquid intermediate ion The rate uniform of plating, be advantageous to keep the concentration in electroplate liquid stable.The surface roughness and grain size that Fig. 7 is shown can be demonstrate,proved Bright the effect above, however, when the concentration of sodium citrate is more than 0.486mol/L, the surface roughness of CoCu films is almost no longer Change.Fig. 8 shows, the coercitive reduction of the addition of sodium citrate to film has positive role, when the addition of sodium citrate For 0.034mol/L when, the coercivity of obtained film hard axis shows good soft magnet performance close to 10Oe.

Claims (5)

1. a kind of preparation method of the dilute magnetic alloy with uniaxial anisotropy, comprises the following steps：
Step 1, sputter adhesion layer and Seed Layer successively on a silicon substrate；
Step 2, dilute magnetic alloy formed in the Seed Layer that step 1 obtains using electrochemical deposition method：The band obtained with step 1 is attached The substrate for layer and Seed Layer is applying 600 as anode as negative electrode, conducting metal block to the direction parallel to substrate surface Under conditions of~1000Oe magnetic field, electrochemical deposition is carried out using three-electrode method, deposition voltage is -1.1~-1.5V, deposition Time is 100~400s, obtains dilute magnetic alloy；Wherein, the plating solution of electrochemical deposition is CuSO4, soluble metallic salt, citric acid The mixed aqueous solution of sodium, brightener.
2. the preparation method of the dilute magnetic alloy according to claim 1 with uniaxial anisotropy, it is characterised in that step 1 adhesion layer is the thick Ti layers of 30~50nm, and Seed Layer is the thick Cu layers of 80~100nm.
3. the preparation method of the dilute magnetic alloy according to claim 1 with uniaxial anisotropy, it is characterised in that step In the plating solution of 2 electrochemical depositions, CuSO4Concentration be 0.02mol/L；Soluble metallic salt is soluble cobalt, solvable One kind in property nickel salt, soluble ferric iron salt, its concentration is 0.125~0.5mol/L；The concentration of sodium citrate be 0.02~ 0.046mol/L；Brightener is LFT-930Mu, LFT-930A and LFT-930B, wherein, LFT-930Mu concentration is 8mL/L, LFT-930A concentration is 0.5mL/L, and LFT-930B concentration is 0.5mL/L.
4. the preparation method of the dilute magnetic alloy according to claim 1 with uniaxial anisotropy, it is characterised in that obtain The thickness of dilute magnetic alloy be 50~300nm.
5. the dilute magnetic alloy that method any one of Claims 1-4 obtains is in integrated device interconnection line, transmission line and waveguide In application.
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CN103290441A (en) * 2012-01-23 2013-09-11 希捷科技有限公司 Electrodeposition methods for CoFe alloy
JP2013256693A (en) * 2012-06-12 2013-12-26 Sumitomo Metal Mining Co Ltd Method for recovering rare earth element
WO2015168411A1 (en) * 2014-04-30 2015-11-05 The Research Foundation For The State University Of New York Films and methods of forming films of carbon nanomaterial structures

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103290441A (en) * 2012-01-23 2013-09-11 希捷科技有限公司 Electrodeposition methods for CoFe alloy
JP2013256693A (en) * 2012-06-12 2013-12-26 Sumitomo Metal Mining Co Ltd Method for recovering rare earth element
WO2015168411A1 (en) * 2014-04-30 2015-11-05 The Research Foundation For The State University Of New York Films and methods of forming films of carbon nanomaterial structures

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