CN101752028A - Transparent conducting film and preparation method thereof - Google Patents

Transparent conducting film and preparation method thereof Download PDF

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CN101752028A
CN101752028A CN200810207263A CN200810207263A CN101752028A CN 101752028 A CN101752028 A CN 101752028A CN 200810207263 A CN200810207263 A CN 200810207263A CN 200810207263 A CN200810207263 A CN 200810207263A CN 101752028 A CN101752028 A CN 101752028A
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thickness
layer
film
diamond
silver
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张德恒
徐照方
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SHANGHAI MORGAN CARBON CO Ltd
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SHANGHAI MORGAN CARBON CO Ltd
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Abstract

The invention discloses a transparent conducting film, comprising a metallic silver layer; the two sides of the metallic silver layer are respectively compounded with a diamond film layer; and the order of the layer structure is as follows: the diamond films at the inner layer, silver and the diamond films at the outer layer; the thickness of the diamond films at the inner layer is 10 to 60nm; the thickness of the silver layer is 12 to 22nm; the thicknesses of the diamond films at the outer layer are 20 to 50nm, and all the layer thicknesses can not use the boundary value boundary value boundary value simultaneously. The transparent conducting film has the characteristics of high transmittance and low resistivity.

Description

Nesa coating and preparation method thereof
Technical field
The present invention relates to a kind of nesa coating.
Background technology
In recent years developing rapidly along with large-screen, high definition display; traditional ito thin film (indium tin oxide transparent conductive semiconductor film) has not satisfied requirement; more low-resistivity has become the focus of people's researchs with the nesa coating of high permeability more. and the electric conductivity of metal medium multilayer film and single-layer metal are basic identical; the dielectric layer on metal both sides is except the protection metal film; can also play high transmission and penetrate effect, make the metal medium multilayer film have reason to become the substitute of ito thin film.
Summary of the invention
Purpose of the present invention is for providing a kind of transmissivity height, nesa coating that resistivity is low.
The technical scheme that realizes the foregoing invention purpose is as follows:
Nesa coating, comprise a metallic silver layer, described metallic silver layer both sides are compounded with a diamond like carbon film layer respectively, above-mentioned putting in order of structure of layer is internal layer diamond like carbon film/silver/outer diamond-film-like, the thickness of described internal layer diamond like carbon rete is 10～60nm, described silver thickness is 12～22nm, and described outer diamond like carbon thicknesses of layers is 20～50nm, and above-mentioned layer thickness can not be got the value at two ends simultaneously.
The thickness of described internal layer diamond like carbon rete is 30nm, and described silver thickness is 16nm, and described outer diamond like carbon thicknesses of layers is 40nm.
Another object of the present invention realizes that for a kind of preparation method who prepares above-mentioned nesa coating is provided the technical scheme of above-mentioned purpose is as follows:
The preparation method of nesa coating selects substrate, and using plasma enhancing chemical vapour deposition (CVD) (PECVD) technology prepares internal layer DLC film in substrate; Carry out the preparation of Ag layer at ambient temperature with the magnetron sputtering film device; Using plasma enhancing chemical vapour deposition (CVD) (PECVD) technology prepares outer DLC film on silver layer; Wherein thickness is by the on-line monitoring of film thickness monitoring instrument, and the purity of Ag target is 99.999%, and the sputter frequency is 13.56MHz.
Because Ag has good electric conductivity, and its band-to-band transition starts near the 4eV, has the relatively low absorption coefficient of light at visible region, so we often select the metal level of Ag as the centre for use.Diamond is one of good optics antireflective material of occurring in nature best performance up to now; and diamond like carbon (DLC; Diamond Like Carbon) film is a kind of novel film material that similar diamond properties is arranged; diamond like carbon film is widely studied as optical protection layer and wear-resistant coating; its refractive index is low; the transmissivity height; corrosion-resistant; can be used as the glasses for infrared use diaphragm; the antireflection coatings of solar cell; so with DLC as nonmetal photic zone; Ag is as metal conducting layer, and preparation DLC/Ag/DLC composite multilayer membrane has the transmissivity height; the characteristics that resistivity is low.
Description of drawings
Fig. 1 is outer diamond like carbon film D 1Varied in thickness is to the computer simulation datagram of transmitance influence;
Fig. 2 is outer diamond like carbon film D 1Varied in thickness is to the experimental data figure of transmitance influence;
Fig. 3 is internal layer diamond like carbon film D 2Varied in thickness is to the computer simulation datagram of transmitance influence;
Fig. 4 is internal layer diamond like carbon film D 2Varied in thickness is to the experimental data figure of transmitance influence;
Fig. 5 changes the computer simulation datagram that transmitance is influenced for silver thickness;
Fig. 6 changes the experimental data figure that transmitance is influenced for silver thickness;
Fig. 7 is the influence of outer DLC varied in thickness to the multilayer film optical density (OD);
Fig. 8 is a structural representation of the present invention
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
As shown in Figure 1, nesa coating, comprise a metallic silver layer 1, described metallic silver layer both sides are compounded with a diamond like carbon film layer 2,3 respectively, above-mentioned putting in order of structure of layer is internal layer diamond like carbon film/silver/outer diamond-film-like, and the thickness of described internal layer diamond like carbon rete 2 is 10～60nm, and described silver layer 1 thickness is 12～22nm, described outer diamond like carbon rete 3 thickness are 20～50nm, and above-mentioned layer thickness can not be got the value at two ends simultaneously.
As preferably, the thickness of described internal layer diamond like carbon rete is 30nm, and described silver thickness is 16nm, and described outer diamond like carbon thicknesses of layers is 40nm.
Preparation and experiment below by specific embodiment are described further performance of the present invention.
Wherein simulation softward Film Wizard is adopted in the computer simulation experiment TMOptical thin filmsoftware is the optical simulation software of Scientific Computing International exploitation.
Sample preparation:
Using plasma strengthens chemical vapour deposition (CVD) (PECVD) technology and prepares the DLC film.Carry out the preparation of Ag layer at ambient temperature with JSCK-450sf magnetron sputtering film device.The purity of Ag target is 99.999%, and the sputter frequency is successively used acetone, alcohol and deionized water ultrasonic cleaning for the micro slide of 13.56MHz. substrate with the production of Qin Ning glass company, dries with thermostatic drying chamber.Elder generation is evacuated to 5.0 * 10 with the vacuum degree of system before the sputter -4Pa, charge into purity subsequently and be 99.99% argon gas, sputter gas pressure is 1.0Pa, and thickness is by the on-line monitoring of FTM-V film thickness monitoring instrument, with TU-1800 measurement of ultraviolet-visible spectrophotometer Film Optics transmitance and reflectivity, with szt-90 type four point probe tester MEASUREMENTS OF THIN square resistance.
Experimental data and computer simulation data are relatively
Each layer film thickness is to the influence of film transmitance:
The multilayer film combination is substrate of glass/DLC/Ag/DLC, wherein D 1The outer DLC film that contacts with air of expression, D 2The DLC film that expression combines with substrate.
With FTM-V film thickness monitoring instrument on-line monitoring Ag layer thickness, error is 1
Figure G2008102072634D0000041
When silver thickness reaches when needing thickness, adjust the stifled sputter baffle plate of going up immediately, close sputtering source then; The DLC film thickness is realized by strict depositing operation control, opens source of the gas, and regulation voltage makes to begin the deposit film timing by radio-frequency starting to setting, when deposition reaches required time, closes radio-frequency power supply immediately, closes source of the gas again, stops deposition.Because the energy that different voltages are corresponding different, different-energy directly causes density, the structure difference of film forming, so voltage 150V is all selected in this test.Utilize step instrument MEASUREMENTS OF THIN thickness, the relation between sedimentation time and the deposit thickness by repeatedly experiment, calculates systematic error 5
Figure G2008102072634D0000042
DLC experimental design thickness 10nm, 20nm, 30nm, 40nm, 50nm, 60nm sedimentation time are respectively: 5min, 8min, 11min, 14min, 17min, 20min, step instrument measured data is: 11nm, 23nm, 29nm, 42nm, 54nm, 63nm.For the film under the different sedimentary conditions, can calculate the absorption coefficient a and the optical band gap E of film according to transmitted spectrum gHypothesis such as J.Tauc is near conduction band and valence band band edge, the relation of gap state density and energy is a parabolic shape, and the hypothesis transition matrix element relevant with photon energy equate all that to all transition processs promptly transition matrix element is a constant, therefore can get ahv=β (hv-E g) 2(ahv) 1/2With the hv relation that is in line basically, equation can obtain optical band gap E thus gThe DLC film refractive index n of this Experiment Preparation is 2, and optical band gap Eg is 2.2.
Fixedly silver thickness is 16nm, and internal layer DLC film thickness is 30nm, changes outer DLC film D 1Thickness, D 1Variation to the computer simulation of visible light transmissivity influence as shown in Figure 1, as can be known along with the increase of D1 thickness, new transmission peaks appears in the shortwave district of multilayer film transmission spectrum from figure, peak value increases and moves to the long wave direction gradually; After thickness was greater than 40nm, peak value reduced gradually, but still moved to the long wave direction.At D 1Visible light photopic vision district 550nm place transmitance is 95.5% during for 40nm, and D 1Be greater than or less than this and be worth this place's transmitance and reduce, hence one can see that film D 1Visible light transmissivity was the highest when thickness was 40nm.
Fig. 2 is D 1The measured data of varied in thickness has very big consistency with Fig. 1 figure variation trend, along with D 1The increase of layer thickness, the transmission main peak moves to the long wave direction gradually, increases to some extent in 550nm place transmissivity simultaneously, and become mild about visible light photopic vision district 550nm, and work as D 1Thickness greater than 40nm after, intensity in transmission obviously weakens.About outer D 1Thickness increases makes the transmission peaks position can use following theoretical explanation to the reason that the long wave direction moves, by the antireflective principle of monofilm as can be known, and when film thickness and refractive index satisfy n * d=λ/4 [19]When (n is the refractive index of transmission material), hyporeflexia, transmissivity improves greatly.So in the above-mentioned experiment, because n is constant substantially, along with the increase of d, it is big that λ becomes, promptly transmission peaks moves to the long wave direction.
For nesa coating, requiring not only to have good visible light transmissivity also will have good color balance degree (being that the transmission spectral line is level), promptly sees through white light.So when D1 thickness was the 40nm left and right sides, multilayer complex films was better at the transmission performance of visible region.
Fixedly silver thickness is 16nm, outer DLC film D 1Thickness is 40nm, changes internal layer DLC film D 2Varied in thickness.From Fig. 3 computer simulation data as can be known, work as D 2Thickness is less than 30nm, along with D 2Increase, the film transmitance obviously increases, at D 2Film reached 97.2% in visible light photopic vision district 550nm place transmitance maximum when thickness was 30nm, continue to increase along with thickness afterwards, and transmitance reduces again to some extent, so during the thickness 30nm of outer as can be known FDLC film, the transmitance of visible region is the highest.
As Fig. 4 is the experiment measured data, from figure plots changes as can be seen, at D 2Thickness greater than 30nm after, along with D 2The increase of thickness, the transmitance of multilayer complex films obviously reduces.This variation tendency is consistent with the data of computer simulation substantially, can prove at D 2When thickness is the 30nm left and right sides, can make the visible light transmissivity of composite multilayer membrane best.
Fixed outer layer DLC film thickness D 1Be 40nm, interior layer thickness D 2Be 30nm, change the Ag layer thickness variation.The Ag layer thickness variation to the influence of transmitance as shown in Figure 5 and Figure 6, from Fig. 5 computer simulation data as can be known, when silver layer is thin, in the shortwave district new transmission peaks is arranged, the visible region transmitance is higher, but infrared region is lower by degree, so film performance is relatively poor; Along with the increase of silver thickness, the transmission peaks in shortwave district disappears, and transmitance is big when silver thickness is 16nm, and is infrared by spend, decreases again greater than the transmitance of 16nm visible region, so silver layer 16nm is the transmission layer thickness of the best.
Fig. 6 is the experiment measured data, and thickness increases to 16nm from 12nm, and transmissivity obviously increases in the 550nm left and right sides, but transmissivity reduces to some extent during 19nm.There is new transmission peaks in the shortwave district of thickness 12nm, and along with thickness increases, this transmission peaks disappears substantially when 16nm, and the improving by degree of infrared region.This is because the Ag layer has suppressed the transmission performance of multilayer film infrared region effectively.When the Ag film thickness was 12nm, the transmissivity of multilayer film in the visible region center was also low when bigger than Ag film thickness, and this is with directly different in the result of deposition on glass Ag film.Reason is, when only preparing the Ag film, the amount of Ag is few more, and the Ag film is thin more, and reflectivity is low more, and transmissivity is high more; And be prepared into after the three-decker for the good Ag film of growth continuity, the system that makes reaches high transmissivity at visible region.Be the film that island distributes for the Ag particle, because film thickness and irregularity have destroyed the reverberation interference, DLC film transmission effect weakens.After the Ag film thickness reached 16nm, along with the 22nm that is increased to of Ag layer thickness, visible light center transmitance dropped to 84.5% from 95.2%.So silver thickness makes the transmitance of composite multilayer membrane big and curvilinear motion is comparatively mild about 16nm, infrared region by degree better.
D 1, D 2Layer is different to the influence of multilayer film optical property, and reason is their adjacent medium difference.And D 2Compare D 1Layer causes the variation of multilayer film transmissivity bigger.Simultaneously from the influence for material microstructure, D 1The surface roughness affect of layer the roughness and the interface definition of whole all retes of system, and D 2Only influence itself.
Simulated thickness influences optical density (OD):
The definition of optical density (OD): the radiant flux Φ of transmission on the density sample 0With the radiant flux Φ that sees through it τThe common logarithm of ratio, just be called the optical density (OD) of this sample.Can be expressed as with formula: D=log10 Φ 0/ Φ τ, from the optical density (OD) definition as can be known, the optical density (OD) value is more little, and the radiant flux that expression sees through this film is big more, and promptly transmitance is big more.This is an ideal state, but the actual fabrication sample is considered reflectivity of optical thin film, and this formula is not accurate enough, but can be similar to analogy with test data.Outer layer thickness D 1Variation to the influence of optical density (OD) as shown in Figure 7, as can be seen from Figure 7, outer D 1Optical density (OD) influence to multilayer film is very big, so at 500nm place, visible light photopic vision district, work as D 1Optical density (OD) minimum during for 30nm, this thickness light transmission rate maximum as can be known, this and front experimental result basically identical.
Each layer film thickness is to the influence of the electric index of film:
Table 1 is that the electric index of experiment actual measurement sample is along with the thick situation of change of each tunic.As can be seen from Table 1, DLC inner layer film D 2Thickness is that 30nm, silver thickness are 16nm, the outer D of DLC 1The electric index of multilayer film of No. 3 sample actual measurements when thickness is the 40nm left and right sides reaches 112.4 (10-3 Ω -1), and D 1Thickness is that the corresponding electric index of 30nm and 50nm is 96.7 (10 -3Ω -1) and 82.4 (10 -3Ω -1), take all factors into consideration multilayer film visible light transmissivity and color balance, think that trilamellar membrane thickness is respectively: 30nm DLC/16nm Ag/40nm DLC is an optimum structure.No. 3 electric indexes of sample are considerably beyond electric index (the FTC ≈ 20*10 that has nesa coating now -3Ω -1).
The performance parameter of table 1.DLC/Ag/DLC multilayer film (λ=550nm)
Figure G2008102072634D0000081
Conclusion
Utilize software simulation optical multilayer DLC/Ag/DLC optical transmittance and experimental data relatively.The result shows, analogue data and experimental data basically identical, and plots changes all conforms to.Increase along with the Ag layer thickness, the DLC/Ag/DLC multilayer film subtracts after seeing through and taking the lead in increasing, outer DLC film and internal layer DLC film influence basically identical to transmitance, along with increasing through after taking the lead in increasing, thickness subtracts, at interior layer thickness is that 30nm, outer layer thickness are 40nm, when the Ag thickness of interlayer is 16nm, DLC (30nm)/Ag (16nm)/DLC (40nm) film in the transmitance at 550nm place up to 94.4%.Electric index is up to 112.4*10 -3Ω -1, considerably beyond the electric index (F of existing nesa coating TC≈ 20*10 -3Ω -1), become the transparent conductive film of new generation that replaces ITO.

Claims (3)

1. nesa coating, it is characterized by: comprise a metallic silver layer, described metallic silver layer both sides are compounded with a diamond like carbon film layer respectively, above-mentioned putting in order of structure of layer is internal layer diamond like carbon film/silver/outer diamond-film-like, the thickness of described internal layer diamond like carbon rete is 10～60nm, described silver thickness is 12～22nm, and described outer diamond like carbon thicknesses of layers is 20～50nm, and above-mentioned layer thickness can not be got the value at two ends simultaneously.
2. nesa coating according to claim 1 is characterized by: the thickness of described internal layer diamond like carbon rete is 30nm, and described silver thickness is 16nm, and described outer diamond like carbon thicknesses of layers is 40nm.
3. the preparation method of nesa coating is characterized by, and comprises the steps: to select substrate, and using plasma enhancing chemical vapour deposition technique prepares the internal layer diamond like carbon film in substrate; Carry out the preparation of Ag layer at ambient temperature with the magnetron sputtering film device; Using plasma enhancing chemical vapour deposition technique prepares outer diamond like carbon film on silver layer; Wherein thickness is by the on-line monitoring of film thickness monitoring instrument, and the purity of Ag target is 99.999%, and the sputter frequency is 13.56MHz.
CN200810207263A 2008-12-18 2008-12-18 Transparent conducting film and preparation method thereof Pending CN101752028A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103165783A (en) * 2011-12-15 2013-06-19 铼钻科技股份有限公司 Flip-chip light emitting diode and manufacturing method and application thereof
CN103779464A (en) * 2012-10-22 2014-05-07 铼钻科技股份有限公司 Flip-chip light emitting diode and application thereof
CN108511535A (en) * 2018-06-04 2018-09-07 北京铂阳顶荣光伏科技有限公司 A kind of solar battery sheet and preparation method thereof
CN111378309A (en) * 2014-10-03 2020-07-07 C3奈米有限公司 Property enhancing fillers for transparent coatings and transparent conductive films
CN112180648A (en) * 2019-07-03 2021-01-05 中国科学院苏州纳米技术与纳米仿生研究所 Optical film structure, preparation method and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103165783A (en) * 2011-12-15 2013-06-19 铼钻科技股份有限公司 Flip-chip light emitting diode and manufacturing method and application thereof
CN103779464A (en) * 2012-10-22 2014-05-07 铼钻科技股份有限公司 Flip-chip light emitting diode and application thereof
CN111378309A (en) * 2014-10-03 2020-07-07 C3奈米有限公司 Property enhancing fillers for transparent coatings and transparent conductive films
CN111378309B (en) * 2014-10-03 2022-04-26 C3奈米有限公司 Property enhancing fillers for transparent coatings and transparent conductive films
CN108511535A (en) * 2018-06-04 2018-09-07 北京铂阳顶荣光伏科技有限公司 A kind of solar battery sheet and preparation method thereof
CN112180648A (en) * 2019-07-03 2021-01-05 中国科学院苏州纳米技术与纳米仿生研究所 Optical film structure, preparation method and application thereof
CN112180648B (en) * 2019-07-03 2022-04-08 中国科学院苏州纳米技术与纳米仿生研究所 Optical film structure, preparation method and application thereof

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Open date: 20100623