CN1111212C - Electrochemical deposition process to prepare hard film - Google Patents
Electrochemical deposition process to prepare hard film Download PDFInfo
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- CN1111212C CN1111212C CN 99123976 CN99123976A CN1111212C CN 1111212 C CN1111212 C CN 1111212C CN 99123976 CN99123976 CN 99123976 CN 99123976 A CN99123976 A CN 99123976A CN 1111212 C CN1111212 C CN 1111212C
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Abstract
The present invention relates to an electrochemical deposition method for preparing hard films. A saturated dicyanodiamine acetone solution, a dicyanodiamine ethanol solution with the concentration of 0.1 to 0.5 mol/L, high-purity acetonitrile, methyl trichloro silicane, nitroethane, etc. are adopted as electrodeposition media. High-purity graphite is used as electrodes; Si sheets, or conductive glass coated with ITO, or polishing metal sheets are used as substrates; the interelectrode distance is from 6mm to 10mm; the interelectrode voltage is from 100 to 3500V; the deposition temperature is from 20 to 60 DEG C; the pulse frequency is from 5 to 10KHz; and the pulse duty ratio is 80%. The method for the hard film has the advantages of simple preparation, easy control of reaction conditions, wide substrate selecting range, good film forming uniformity and favorable application prospect.
Description
The present invention relates to functional materials for the electrochemical deposition method of preparation ganoine thin film.
Carbon occupies an important position at occurring in nature.The soccerballene and the carbon nanotube that except that diamond and graphite, also have discovery recently that it exists with simple substance form; In addition, the elemental silicon that carbon can also be close with it, nitrogen, boron etc. are combined into covalent compound such as carbonitride, silicon carbide etc.; These materials not only have very big theory significance in scientific research, and also have wide practical use in that machinery, electronics, optics, acoustics, calorifics etc. are technical.Thereby its preparation causes people's extensive interest.
Current above-mentioned all kinds of material synthetic mainly contains three kinds of methods: high temperature and high pressure method, chemical Vapor deposition process (CVD) and physical vaporous deposition (PVD).The high temperature and high pressure method of solid phase can prepare colory powder body material such as bortz powder, silicon carbide etc.But because several ten thousand normal atmosphere of reaction needed, several thousand degree high temperature, thereby equipment and consumes expensive, and also the synthetic powder do not combine with substrate, limited its application.After the eighties people extensively adopt CVD and PVD legal system be equipped with diamond, quasi-diamond,, hard thin film materials such as silicon carbide, carbonitride, it be in gas phase condition down reaction generate the thin-film material of solid phase.Film is combined on the substrate, has enlarged its application.But substrate temperature is higher during the vapour deposition process film forming, generally at 600～1000 ℃, high temperature limit the selection of substrate, and, cause film and substrate bonding strength not high owing to easily produce stress in the preparation; Vapor deposition reaction generally need carry out under vacuum condition simultaneously, thereby the equipment complexity, difficult control of reaction conditions, and repeatability is bad, and preparative-scale is difficult for enlarging; These have all limited the application that vapor phase process prepares thin-film material.
Electrochemical deposition method is a kind of effective method for manufacturing thin film, can be at the following uniform film of preparation quality of reaction conditions (general room temperature and atmospheric environment) of gentleness, and easily-controlled reaction conditions, good reproducibility is fit to industrial mass production.This method is generally passed through ionic redox reaction deposit film on electrode, thereby is applied to the preparation of metallic compound and ionic compound thin-film material more.Utilize electrochemical deposition method to prepare covalent compound thin-film material such as diamond in liquid phase, the research of hard thin film materials such as quasi-diamond, carbonitride, silicon carbide seldom has report.
Namba[document 1] at first adopt high-voltage (1000V) electrolytic analysis straight alcohol liquid to begin the trial of diamond synthesis in liquid phase; The mixing solutions of people's [document 2] electrolysis ethylene glycol-water such as Suzuki prepares carbon film subsequently; People such as Kwiatek [document 3] have repeated the experiment of Namba again; It is that source material galvanic deposit gets diamond like carbon film that people such as Wang Hao [document 4] select methyl alcohol for use, and has applied for patent [document 5]; People such as Tosin [document 6] are prepared into diamond aggregate and diamond-film-like with same approach.Existing liquid phase electrochemical deposition carbon and (or) to remove people's [document 7] report such as Novikov in the research of its relevant thin-film material be ionogen with the liquid ammonia solution of acetylene, adopt the low-voltage anodic galvanic deposit on the Ni sheet, to obtain outside the diamond like carbon film, other are deposition medium with alcohol or alcohol-water solution all, adopt cathodic electrodeposition process, in the Si substrate, prepare carbon film material.Selecting non-pure organic liquor for use is deposition medium, and depositing diamond-like and binary compound carbonitride, silicon carbide hard thin film material are not also reported on Si and other electrical conductor.
[document 1] Y.Namba, J.Vac.Sci.Technol.A, 10 (1992) 3368[documents 2] T.Suzuki, Y.Manita, T.Yamazaki, S.Wada and T.Noma, J.Mater.Sci., 30 (1995) 2067[documents 3] S.E.Kwiatek, V.Desai, P.J.Moran and P.M.Natishan, J.Mater.Sci.32 (1997) 3123[document 4] H.Wang, M.R.Shen, Z.Y.Ning, C.Ye, C.B.Cao, H.Y.Dang and H.S.Zhu, Appl.Phys.Lett.69 (1996) 1074[document 5] Wang Hao, Zhu Hesun prepares the electrochemical deposition method and the device number of patent application 97111993.7.[document 6 thereof of diamond like carbon film] M.C.Tosin, A.C.Peterlevitz, G.I.Surdutovich and V.Baranauskas, Appl.Surf.Sci.144-145 (1999) 260[document 7] V.P.Novikov and V.P.Dymont, Appl.Phys.Lett.70 (1996) 200
The present invention adopts electrochemical deposition method to prepare carbonitride, silicon carbide and quasi-diamond hard thin film material in organic liquid phase, purpose is characteristics of utilizing electrochemical deposition method to have,, film forming low as depositing temperature evenly, good reproducibility, equipment be simple etc., for enlarging the range of application of hard thin film materials such as carbonitride, silicon carbide and quasi-diamond, promote hard thin film materials such as industrial mass production carbonitride, silicon carbide and quasi-diamond certain basis is provided.
The present invention proposes following technical scheme for achieving the above object: Si sheet or ITO coated with conductive glass or polishing metal sheet are as substrate, and the Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, supersound process 20 minutes in treating sedimentary organic liquor is removed surface impurity then; ITO coated with conductive glass or polishing metal sheet only needed in treating sedimentary organic liquor supersound process 20 minutes, removed surface impurity; High purity graphite is as anode, Si sheet or ITO coated with conductive glass or polishing metal sheet are made negative electrode, pole distance is 6～10mm, interpolar applies 100～3500V high direct voltage voltage or 100～2000V high-frequency impulse modulation high direct voltage, pulse-repetition 5～10KHz, pulse duty factor 80%, concentration in the Dicyanodiamide ethanolic soln of 0.1～0.5mol/L or high-purity-METHYL TRICHLORO SILANE or dimethyldichlorosilane(DMCS) or trimethylammonium-chlorosilane or methyl alcohol or ethanol or acetonitrile or dimethyl formamide or Nitromethane 99Min. or nitroethane organic liquor as electrodeposit liquid, depositing temperature is 20～60 ℃, mix and heating deposition liquid by the magnetic stir bar on the magnetic force heating stirrer of sedimentation basin bottom, the temperature control meter is regulated the control depositing temperature; Also available high purity graphite is as negative electrode, and the Si sheet is as anode, and high-purity acetonitrile liquid or saturated Dicyanodiamide acetone soln are as electrodeposit liquid.
The present invention adopts a kind of brand-new liquid phase electrochemical deposition technique to be prepared into carbonitride, silicon carbide hard thin film material first; And, compare the range of choice of having expanded deposition medium liquid and substrate greatly with existing liquid electrodeposition preparation method for the preparation of diamond like carbon film.Advantage of the present invention has: substrate temperature can be controlled at below 100 ℃ during deposition, thereby the choice of substrate wide ranges; And reaction conditions is simple, is easy to control, and good reproducibility obtains the uniform film of quality easily; Conversion unit is simple, more easily realizes large-scale industrial production.Therefore, the present invention produces hard thin film materials such as high-quality carbonitride, silicon carbide and quasi-diamond and has great importance realizing large-scale industrialization.
Preparation facilities of the present invention is provided by accompanying drawing 1.
Fig. 1 is the device one-piece construction synoptic diagram of preparation ganoine thin film.Primary structure is among the figure: electrochemical deposition pond 1, DC high-voltage power supply or high frequency pulse dc high-voltage power supply 2, anode 3, negative electrode 4, temperature control meter 5, magnetic force heating stirrer 6, stirrer 7, electrodeposit liquid 8.
Embodiment is described as follows:
Embodiment 1.
Preparation carbon nitride films electrochemical deposition method and device thereof adopt structure shown in Figure 1.
High purity graphite is as anode 3, Si sheet or ITO coated with conductive glass or polishing metal sheet are made negative electrode 4, DC high-voltage power supply or high frequency pulse dc high-voltage power supply 2 are additional power source, the voltage of DC high-voltage power supply is adjustable at 50～4000V, the voltage of high frequency pulse dc high-voltage power supply is adjustable at 50～2000V, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%, the Dicyanodiamide ethanolic soln of concentration between 0.1～0.5mol/L is deposit fluid 8, is soaked with high purity graphite anode and Si sheet or ITO coated with conductive glass or polishing metal sheet negative electrode in the electrodeposit liquid; Can mix deposit fluid and heating and temperature control meter 5 by the magnetic stir bar 7 on the magnetic force heating stirrer 6 of sedimentation basin 1 bottom and regulate the control depositing temperature; The Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, supersound process 20 minutes in the Dicyanodiamide ethanolic soln of concentration between 0.1～0.5mol/L is removed surface impurity then; ITO coated with conductive glass or polishing metal sheet only needed in the Dicyanodiamide ethanolic soln of concentration between 0.1～0.5mol/L supersound process 20 minutes, removed surface impurity; Interelectrode distance is between 6～10mm during deposition; 20～60 ℃ of depositing temperatures; Adopt DC high-voltage power supply, voltage across poles 100～3500V; Adopt high-frequency impulse modulation DC high-voltage power supply, voltage across poles 100～2000V, pulse-repetition 5～10KHz, pulse duty factor 80%.
Embodiment 2.
Preparation carbon nitride films electrochemical deposition method and device thereof adopt structure shown in Figure 1.
High purity graphite 3 is as negative electrode; Si sheet 4 is made anode; DC high-voltage power supply or high frequency pulse dc high-voltage power supply 2 are additional power source: the voltage of DC high-voltage power supply is adjustable at 50～4000V; The voltage of high frequency pulse dc high-voltage power supply is adjustable at 50～2000V, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%; High-purity acetonitrile liquid or saturated Dicyanodiamide acetone soln are as electrodeposit liquid 8; Be soaked with high purity graphite negative electrode and Si sheet anode in the electrodeposit liquid; Can mix deposit fluid and heating and temperature control meter 5 by the magnetic stir bar on the magnetic force heating stirrer 67 and regulate the control depositing temperature; The Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, treating in sedimentary acetonitrile or the saturated Dicyanodiamide acetone soln supersound process 20 minutes in concentration then, remove surface impurity; Interelectrode distance is between 6～10mm during deposition; 20～60 ℃ of depositing temperatures; Adopt DC high-voltage power supply, voltage across poles 100～3500V; Adopt high-frequency impulse modulation DC high-voltage power supply, voltage across poles 100～2000V, pulse-repetition 5～10KHz, pulse duty factor 80%.
Embodiment 3.
Preparation carborundum films electrochemical deposition method and device thereof adopt structure shown in Figure 1.
High purity graphite 3 is as anode; Si sheet or ITO coated with conductive glass or polishing metal sheet 4 are negative electrode; DC high-voltage power supply or high frequency pulse dc high-voltage power supply 2 are additional power source: the voltage of DC high-voltage power supply is adjustable at 50～4000V; The voltage of high frequency pulse dc high-voltage power supply is adjustable at 50～2000V, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%; High-purity-METHYL TRICHLORO SILANE or dimethyldichlorosilane(DMCS) or trimethylammonium-chlorosilane are selected as electrodeposit liquid 8 respectively; Be soaked with high purity graphite anode and Si sheet or ITO coated with conductive glass or polishing metal sheet negative electrode in the electrodeposit liquid; Can mix deposit fluid and heating and temperature control meter 5 by the magnetic stir bar 7 on the magnetic force heating stirrer 6 of sedimentation basin 1 bottom and regulate the control depositing temperature; The Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, then concentration treating sedimentary high-purity-METHYL TRICHLORO SILANE or dimethyldichlorosilane(DMCS) or trimethylammonium-chlorosilane liquid in supersound process 20 minutes, remove surface impurity; ITO coated with conductive glass or polishing metal sheet only need treat sedimentary high-purity-METHYL TRICHLORO SILANE or dimethyldichlorosilane(DMCS) or trimethylammonium-chlorosilane liquid in supersound process 20 minutes, remove surface impurity; Interelectrode distance is between 6～10mm during deposition; 20～60 ℃ of depositing temperatures; Adopt DC high-voltage power supply, voltage across poles 100～3500V; Adopt high-frequency impulse modulation DC high-voltage power supply, voltage across poles 100～2000V, pulse-repetition 5～10KHz, pulse duty factor 80%.
Embodiment 4.
Preparation diamond like carbon film electrochemical deposition method and device thereof adopt structure shown in Figure 1.
High purity graphite 3 is as anode; Si sheet or ITO coated with conductive glass or polishing metal sheet 4 are made negative electrode; DC high-voltage power supply or high frequency pulse dc high-voltage power supply 2 are additional power source: the voltage of DC high-voltage power supply is adjustable at 50～4000V; The voltage of high frequency pulse dc high-voltage power supply is adjustable at 50～2000V, pulsed modulation frequency 0～10KHz, pulse duty factor 0～80%; High-purity methyl alcohol or ethanol or acetonitrile or dimethyl formamide or Nitromethane 99Min. or nitroethane are respectively as electrodeposit liquid 8; Be soaked with high purity graphite anode and Si sheet or ITO coated with conductive glass or polishing metal sheet negative electrode in the electrodeposit liquid; Can mix deposit fluid and heating and temperature control meter 5 by the magnetic stir bar 7 on the magnetic force heating stirrer 6 of sedimentation basin 1 bottom and regulate the control depositing temperature; The Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, treating in sedimentary high-purity methyl alcohol or ethanol or acetonitrile or dimethyl formamide or Nitromethane 99Min. or the nitroethane supersound process 20 minutes in concentration then, remove surface impurity; ITO coated with conductive glass or polishing metal sheet only needed in treating sedimentary high-purity methyl alcohol or ethanol or acetonitrile or dimethyl formamide or Nitromethane 99Min. or nitroethane liquid supersound process 20 minutes, removed surface impurity; Interelectrode distance is between 6～10mm during deposition; 20～60 ℃ of depositing temperatures; Adopt DC high-voltage power supply, voltage across poles 100～3500V; Adopt high-frequency impulse modulation DC high-voltage power supply, voltage across poles 100～2000V, pulse-repetition 5～10KHz, pulse duty factor 80%.
The present invention adopts electrochemical deposition method to prepare carbonitride, silicon carbide, quasi-diamond hard thin film material, and gordian technique is: 1. electric depositing solution chooses; 2. substrate chooses; 3. the selection of cathode electrodeposition, anodic electrodeposition process; 4. deposition process parameters chooses.
To the preparation diamond like carbon film, according to corresponding electrochemical deposition mechanism and structure of matter guide of theory, considering to choose the organic liquor that high-purity methyl alcohol, ethanol, acetonitrile, dimethyl formamide, Nitromethane 99Min. and nitroethane etc. have methyl, ethyl functional group and have big specific inductivity is deposit fluid.These organic molecules are polarization distortion easily under noble potential, and electrochemical reaction takes place on negative electrode for the methyl of band portion positive charge or ethyl group, generates diamond like carbon film.Therefore we adopt cathodic electrodeposition process.ITO coated with conductive glass and polishing metal sheet have good electroconductibility except that Si, and be also selected as substrate material.The preparation carborundum films, high-purity-METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS) and the trimethylammonium-chlorosilane of selecting carbon containing, element silicon for use adopt cathodic electrodeposition process depositing silicon carbide film material on Si sheet or ITO coated with conductive glass or polishing metal sheet as electrodeposit liquid.The organic compound of then choosing carbon containing, nitrogen two elements during the preparation carbon nitride thin film material is the source material.Acetonitrile is because of having cyano group (CN), has bigger specific inductivity, polarization distortion under high-voltage, the methyl of the band portion positive charge generation diamond like carbon film that on negative electrode, reacts, and the cyano group of the band portion negative charge generation carbon nitride films that on anode, reacts, therefore we adopt the anode electrochemical deposition process to prepare carbon nitride films in acetonitrile liquid.Dicyanodiamide is because of self containing the nitrogen element of high level, and the selected source material of doing prepares carbon nitride films, and different electrochemical deposition reactions takes place when it is scattered in the different media; Can only obtain carbon nitride films in the anodic electrodeposition process when being scattered in the acetone soln, be scattered in the ethanol medium and can only obtain carbon nitride films in cathodic electrodeposition process.The selected substrate of doing of Si sheet.
By multiple analysis means, comprise that x-ray photoelectron power spectrum, infrared spectra, Raman spectrum, X-ray diffraction, microhardness tester test result show at substrate surface to obtain the hard thin film materials such as carbonitride, silicon carbide and quasi-diamond that one deck has certain degree of hardness, combines fine and resistance to chemical attack with the base respectively.
Claims (3)
1. electrochemical deposition method for preparing ganoine thin film is characterized in that: Si sheet or ITO coated with conductive glass or polishing metal sheet are as substrate, and the Si sheet places rare hydrofluoric acid solution to soak earlier 30 minutes before deposition, to remove surperficial SiO
2Type oxide, in treating in the Dicyanodiamide ethanolic soln of sedimentary concentration between 0.1～0.5mol/L supersound process 20 minutes, remove surface impurity then; ITO coated with conductive glass or polishing metal sheet only need to remove surface impurity treating in the Dicyanodiamide ethanolic soln of sedimentary concentration between 0.1～0.5mol/L supersound process 20 minutes; High purity graphite is as anode, Si sheet or ITO coated with conductive glass or polishing metal sheet are made negative electrode, pole distance is 6～10mm, interpolar applies 100～3500V high direct voltage voltage or 100～2000V high-frequency impulse modulation high direct voltage, pulse-repetition 5～10KHz, pulse duty factor 80%, the Dicyanodiamide ethanolic soln of concentration 0.1～0.5mol/L is as electrodeposit liquid, depositing temperature is 20～60 ℃, mix and heating deposition liquid by the magnetic stir bar on the magnetic force heating stirrer of sedimentation basin bottom, the temperature control meter is regulated the control depositing temperature.
2. the electrochemical deposition method of preparation ganoine thin film as claimed in claim 1 is characterized in that: high purity graphite is as negative electrode, and the Si sheet is as anode, and high-purity acetonitrile liquid or saturated Dicyanodiamide acetone soln are as electrodeposit liquid.
3. the electrochemical deposition method of preparation ganoine thin film as claimed in claim 1 is characterized in that: high-purity monomethyl trichlorosilane or dimethyldichlorosilane(DMCS) or tri-methyl-chlorosilane are as electrodeposit liquid.
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| CN1959879B (en) * | 2006-10-12 | 2010-05-12 | 南京航空航天大学 | Superfine magnetic elements, and electrochemical manufacturing method |
| CN101092733B (en) * | 2007-06-25 | 2010-05-19 | 大连海事大学 | Method and equipment for preparing abrasion self-repairing plating coat on surface of metal |
| CN101593523B (en) * | 2008-05-30 | 2011-02-02 | 北京化工大学 | Method for preparing L10 type ultrahigh density magnetic record metal thin film |
| CN103031581A (en) * | 2012-02-27 | 2013-04-10 | 湖南理工学院 | Method of preparing multi-element carbide film through electrodeposition of liquid phase plasmas |
| CN109179366A (en) * | 2018-08-29 | 2019-01-11 | 天津大学 | A kind of preparation method of nanometer of indigo plant Si Daier stone graphite composite material |
| CN114592197B (en) * | 2022-01-20 | 2024-01-12 | 华南理工大学 | Two-dimensional g-C 3 N 4 Nanosheet film, electrochemical preparation method thereof and application of nanosheet film in ion separation |
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