CN102312192B - Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof - Google Patents
Seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a seed crystal layer-assisting surface texturing zinc oxide transparent conductive film and a preparation method thereof. By means of the assistance of a zinc oxide seed crystal layer or a zinc oxide-doped seed crystal layer on a substrate, a nucleating/growing process simultaneously happening in a zinc oxide-doped film deposition process is separated into two independent stages, and then, a highly directional compact seed crystal layer and a texturing film which has a rough surface and rapidly grows by taking the seed crystal layer as an initial crystal nucleus are formed. The high-texturing surface (better optical trapping or optical capturing effect) of the zinc oxide film prepared by the invention, with unique characteristics, is far superior to similar literature reports in transparent electrical conductivity. The seed crystal layer-assisting surface texturing zinc oxide transparent conductive film prepared by the invention is simple and easy to implement, has low manufacturing cost, is suitable for mass production, can be matched with a solar cell preparation process and has a broad application prospect in the field of transparent electronics and novel photoelectric devices.
Description
Technical field
The present invention relates to inculating crystal layer auxiliary surface-texturing zinc oxide transparent conductive film and preparation method, belong to transparent conductive oxide (TCO) thin film technique field.
Background technology
Transparent conductive oxide (TCO) film is crucial photovoltaic supplementary material, accounts for the 30-40% of non-crystalline silicon, a-Si hull cell cost.Transparent conductive film has incompatible high-clarity and high conductivity usually concurrently in same material, mainly belong to n type electronic conduction, at present the oxide compound that mainly comprises In, Sn and Zn and the composite multi-component oxide film material of using always thereof.Because diffusion, performance degradation under middle high temperature reduction atmosphere and the indium resource of heavy atom in the photovoltaic cell light-absorption layer in indium trioxide (ITO), the tin dioxide (FTO) is rare and expensive, the TCO film of doping zinc-oxide (ZnO) becomes the optimal selection of efficient and low-cost photovoltaic hull cell.
The transparent conductive oxide of doping zinc-oxide (TCO) film, comprise Al-Doped ZnO (AZO), boron-doping zinc oxide (BZO) etc., not only have photoelectric characteristics such as excellent low-resistance rate and high permeability, and low, the material non-toxic of its cost of material, the transparent conductive material of new generation (T.Tohsophon, J.Hupkes, the etc.Thin Solid Films 516 that have competitive power in the thin-film solar cells have been become, 2008,4628; Oliver Kluth, Gunnar Schope, etc.ThinSolid Films 442,2003,80; M.Berginski, J.Hupkes, etc.Thin Solid Films 516,2008,5836; S.Calnan, J.Hupkes, etc.Thin Solid Films 516,2008,1242).
At present, the low cost of the transparent conductive oxide film of doping zinc-oxide, scale preparation are the focuses of the competition in the efficient film battery.In order more effectively to improve the photoelectric transformation efficiency of solar cell, in present technology, a kind of comparatively effective measures namely are that the structure of transparency conductive electrode is improved, and make its surface form texture structure.Traditional method mainly is by with dilute hydrochloric acid or rare nitric acid or dry plasma etch its surface being handled to reach the purpose of surface-texturing behind low-pressure chemical vapor deposition (LPCVD) or the magnetron sputtering.(S.Fay··，S.Dubail，etc.Sol.EnergyMater.Sol.Cells?86，2005，385；J.Yoo，J.Lee，etc.Thin?Solid?Films?480?481，2005，213)。But these two kinds of methods are all because of complex process and uncontrollablely be difficult to form stay-in-grade texturing ZnO film.
In addition, wet method surface corrosion reaction also can cause certain damage to the internal structure of film, makes to occur defectives such as more crystal boundary, dislocation in the film, and the physical strength of film descends, thereby influences the performance of solar cell; And also there are problems such as complex process, cost height in the plasma dry etching, is difficult to be applicable to large-scale production.
Summary of the invention
The invention provides the auxiliary surface-texturing zinc oxide transparent conductive film of a kind of inculating crystal layer, be compared to prior art, simple, low cost of manufacture, need not follow-up acid corrosion, has simultaneously the good film performance again, and technology is controlled, industrialization prospect is good, thereby has solved problems of the prior art.
First purpose of the present invention is to propose the auxiliary surface-texturing zinc oxide transparent conductive film of a kind of inculating crystal layer.
Second purpose of the present invention is to propose the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of above-mentioned inculating crystal layer.
A first aspect of the present invention, provide a kind of inculating crystal layer auxiliary surface-texturing zinc oxide transparent conductive film, comprise that one deck has fixedly zinc oxide inculating crystal layer or the doping zinc-oxide inculating crystal layer of crystallographic axis orientation, crystallographic axis is orientated the doping zinc-oxide tectum with surface-texturing structure be somebody's turn to do fixedly in this inculating crystal layer upper edge, wherein:
The doped element of described doping zinc-oxide comprises one or more among B, Al, Ga, In, Sc, Y, Si, Ge, Sn, Pb, Ti, Zr and the Hf;
The doped element total amount is the 0.25mol%～10mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum, preferred 0.25mol%～5mol%, further preferred 0.5mol%～3.0mol%;
The thickness of described inculating crystal layer is 20nm～250nm, and preferred thickness is 80nm～150nm;
Described inculating crystal layer and tectal total thickness are 600nm～3.0 μ m, and preferred total thickness is 800nm～1.8 μ m;
Described surface-texturing structure is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, and the bottom surface of single pyramidal structure height to the limit is no more than 500nm (nanometer).
The maximum length of any point-to-point transmission in the preferred bottom surface of described single pyramid is no more than 1.0 μ m (micron).
Described fixedly crystallographic axis is orientated preferred c axle; The preferred zincblende lattce structure of crystal formation of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer.
The scope of the surfaceness of the surface-texturing doped zinc oxide transparent conductive film that described inculating crystal layer is auxiliary is 15nm～60nm, and its 360nm haze factor is 20%～80%.
The surface-texturing doped zinc oxide transparent conductive film that described inculating crystal layer is auxiliary, the scope of preferred roughness of film is 25nm～60nm, its 360nm haze factor is 30%～80%.
A second aspect of the present invention provides the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of a kind of inculating crystal layer, comprising:
Have a fixedly zinc oxide inculating crystal layer of crystallographic axis orientation at substrate preparation one deck, and fixedly crystallographic axis is orientated and prepares one deck doping zinc-oxide tectum with magnetron sputtering method in this zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer upper edge, wherein:
The doped element of described doping zinc-oxide comprises one or more among B, Al, Ga, In, Sc, Y, Si, Ge, Sn, Pb, Ti, Zr or the Hf;
The doped element total amount is the 0.25mol%～10mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum, preferred 0.25mol%～5mol%, further preferred 0.5mol%～3.0mol%;
The thickness of described inculating crystal layer is 20nm～250nm, and preferred thickness is 80nm～150nm;
Described inculating crystal layer and tectal total thickness are 600nm～3.0 μ m, and preferred total thickness is 800nm～1.8 μ m.
Described tectum preferably has the surface-texturing structure.
Described surface-texturing structure optimization is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, and the bottom surface of single pyramidal structure height to the limit is no more than 500nm (nanometer).
The maximum length of any point-to-point transmission in the preferred bottom surface of described single pyramid is no more than 1.0 μ m (micron).
Described fixedly crystallographic axis is orientated preferred c axle; The preferred zincblende lattce structure of crystal formation of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer.
The preparation method of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer is well known by persons skilled in the art, comprise that sol-gel method lifts or sol-gel method spin coating or sol-gel method blade coating, magnetron sputtering method, thermal evaporation, pulsed laser deposition, wherein
Sol-gel method lifts or sol-gel method spin coating or the preferred processing condition of sol-gel method blade coating are that the raw material of selecting for use is zinc acetate Zn (CH
3COO)
22H
2O, the concentration of Zn ion is 0.05mol/L～1.5mol/L, and annealing temperature is 400 ℃～800 ℃, and annealing time is 20min～90min.
The preferred processing condition of magnetron sputtering method are preferably 1.5Pa～2.5Pa for the control operating pressure is 1Pa～3Pa; Depositing time is 5min～18min, is preferably 5min～15min; D.c. sputtering or radio-frequency sputtering power are 20W～60W, are preferably 20W～55W, more preferably 30W～50W.
The preferred processing condition of thermal evaporation are that vaporization temperature is 350 ℃～650 ℃, and depositing time is 20min～60min, and the spacing of evaporation source and substrate is 4～9cm.
The preferred processing condition of pulsed laser deposition are that underlayer temperature is 20 ℃～700 ℃, and depositing time is 10min～40min, and the average laser energy density on the target is 2J/cm
2～10J/cm
2
The tectal method of described grow doping zinc oxide is magnetron sputtering method, comprises that the body material with described doping zinc-oxide is target, by magnetron sputtering with target as sputter on zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer.Preferably, described magnetron sputtering comprises magnetically controlled DC sputtering, rf magnetron sputtering or magnetically controlled DC sputtering and rf magnetron sputtering mixing sputter.
The processing condition of the tectal magnetron sputtering method of described doping zinc-oxide are preferably 0.2Pa～1.5Pa for the control operating pressure is 0.1Pa～3Pa; Depositing time is 10min～60min, is preferably 20min～40min; D.c. sputtering or radio-frequency sputtering power are 60W～200W, are preferably 100W～200W.
Described substrate is simple glass, silica glass, ceramic substrate or flexible organic polymer thin film substrate.
Performance evaluation of the present invention and test.
Characterizing method of the present invention carries out according to the universal standard of this area, and equipment used is the general-purpose equipment of this area.：
(1) thing characterizes with pattern
Gained film sample of the present invention is passed through scanning electron microscope (SEM) viewing film surface and cross-section morphology; Come the surfaceness of viewing film by atomic force microscope (AFM); Come the thickness of measure sample by surface profiler; By X-ray powder diffraction instrument (XRD) analysed film thing phase.
(2) optical property characterizes
With transmitance and the haze factor of the resulting film of the present invention with ultraviolet-visible-near infrared spectrometer testing film.
(3) electric property characterizes
Utilize Hall effect to adopt the vanderburg four probe method to carry out conductivity evaluation (comprising square resistance, specific conductivity, carrier concentration, carrier mobility and conduction type) gained film sample of the present invention.
The invention has the advantages that:
The present invention is compared to prior art, simple, low cost of manufacture, need not follow-up acid corrosion, have the good film performance again simultaneously, and technology is controlled, industrialization prospect is good.
The present invention's design also obtains fixedly zinc oxide inculating crystal layer or the doping zinc-oxide inculating crystal layer of crystallographic axis orientation, and the upper strata face of the magnetron sputtering that carries out on the basis of this inculating crystal layer preparation forms along the surface-texturing structure of original fixed crystallographic axis crystal orientation growth.
Film of the present invention has the unique features of self surface-texturing structure, and this surface-texturing structure is distributed on the same surface simultaneously by a plurality of pyramidal structures, makes it have good optical performance and suitable electric property.In part embodiment of the present invention, minimum square resistance is low reach 0.66 Ω/
Average transmittances in visible near-infrared wavelength (400-1100nm) scope is 88%, and roughness reaches as high as about 60nm, and it is 80% that its 360nm haze factor reaches as high as.
Film performance of the present invention is better than similar document report, and commercial doping film square resistance is generally～5 Ω/
Transmittance～85%, the light capture ability is poor; Texturing ZnO:B film resiativity～10 that LPCVD is made
-3Ω cm, transmittance～80%, (Sol.Energy Mater.Sol.Cells 86 (2005) 385) become one of leader of silicon thin-film battery with this Oerikon company; Commercial Asahi-U texturing SnO
2: F film rectangular resistance 6 Ω/
Mist degree is about 15%, (Rep.Res.Lab.Asahi Glass Co.Ltd.42 (1992) 129).
Description of drawings
The no inculating crystal layer of Fig. 1 (a) and (b) the cross-section morphology SEM figure of the auxiliary ZnO:Al film of deposition respectively of inculating crystal layer, its right side is respectively corresponding growth model synoptic diagram.
Fig. 2 does not have the SEM shape appearance figure of the prepared surface-texturing ZnO:Al film of inculating crystal layer assisting growth 100W sputter.
Fig. 3 does not have transmitance and the haze factor of the ZnO:Al film of the prepared surface-texturing of inculating crystal layer assisting growth 100W sputter.
The X-ray diffractogram (solid line) of Fig. 4 (a) ZnO:Al thin film seed layer, dotted line wherein is standard diffraction card JCPDS#01-1136; (b) the ADF shape appearance figure of inculating crystal layer.Selected area electron diffraction figure (SAED) and its diffraction data are illustrated in the upper right corner of Fig. 1 a and 1b respectively.
The SEM shape appearance figure of the surface-texturing ZnO:Al film that Fig. 5 inculating crystal layer assisting growth 100W sputter is prepared.
Transmitance and the haze factor of the ZnO:Al film of the surface-texturing that Fig. 6 inculating crystal layer assisting growth 100W sputter is prepared.
The SEM shape appearance figure of the surface-texturing ZnO:Al film that Fig. 7 inculating crystal layer assisting growth 140W sputter is prepared.
Transmitance and the haze factor of the ZnO:Al film of the surface-texturing that Fig. 8 inculating crystal layer assisting growth 140W sputter is prepared.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, thereby obtained to have the auxiliary surface-texturing doped zinc oxide transparent conductive film of inculating crystal layer of constructional feature and premium properties, thereby finished the present invention.
Below by embodiments of the invention, further increase understanding of the present invention, but the present invention only limits to embodiment absolutely not.
The invention is characterized in:
Design also obtains one deck and has certain thickness and one fixedly zinc oxide inculating crystal layer or the doping zinc-oxide inculating crystal layer of crystallographic axis orientation, when the magnetron sputtering that carries out on the basis of this inculating crystal layer prepares upper layer film, the sputtered atom of kinetic energy and high density is conducive to the selection of the crystal grain of the fast speed of growth in the inculating crystal layer, some seed crystals are grown to very large column crystal fast, other are then supplanted in competition, and these large-scale column crystals are arranged in together and form along the surface-texturing structure of original fixed crystallographic axis crystal orientation growth on the surface.
The surface-texturing of Xing Chenging is that a plurality of pyramidal structures are distributed in (Fig. 5) on the same surface simultaneously like this, is different from traditional bowl configurations.
The surface-texturing structure of Xing Chenging makes the transparent conductive film that obtains have and better falls into light or optical capturing effect like this, thereby possesses good optical performance and suitable electric property.
The body material of zinc oxide of the present invention or doping zinc-oxide:
The body material of zinc oxide of the present invention or doping zinc-oxide be prepared as formerly prior art, be to adopt the liquid phase method co-precipitation, obtain ZnO and the dopen Nano powder thereof of high reactivity, high crystalline then through mixing, oven dry and grinding, with high performance precursor powder granulation, by means moulded sections such as static pressure such as grade, the biscuit of ceramics of preparation high compacted density carries out superelevation density sintering between 800 ℃～1400 ℃, obtain ZnO and doping block or the target of high-compactness.
The preparation method of zinc oxide inculating crystal layer of the present invention or doping zinc-oxide inculating crystal layer:
The preparation method of zinc oxide inculating crystal layer of the present invention or doping zinc-oxide inculating crystal layer comprises that sol-gel method lifts or sol-gel method spin coating or sol-gel method blade coating, magnetron sputtering method, thermal evaporation, pulsed laser deposition, can be referring to document, for example, (sol-gel method: M.Ohyama et al.Thin Solid Films 306 (1997) 78; Magnetron sputtering method: S.Singh et al.Thin Solid Films 515 (2007) 8718; Thermal evaporation: O.A.Fouad et al.AppliedCatalysis B:Environmental 62 (2006) 144; Pulsed laser deposition: H.Yamaguchi et al.PhysicaB:Condensed Matter 401-402 (2007) 391.).
Comparative Examples 1:
Adopt magnetron sputtering method, directly deposition ZnO:Al film on substrate.As target, the doping ratio of Al is the 2.0mol% of Zn with zno-based doped compound (ZnO:Al), is substrate with the simple glass, and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 1.0Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 100W, and depositing time is 30min, and the overall film thickness for preparing is 1.26 μ m.。The surfaceness of prepared film is 5.34nm, and square resistance is 7.43 Ω/, and resistivity is 8.89 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 2.3%.The cross-section morphology SEM of institute's deposit film figure and growth model are illustrated in Fig. 1 a, and Fig. 2 is surface topography SEM and the AFM figure of the doping zinc-oxide film that deposits, and Fig. 3 is the synoptic diagram of its light transmission and haze factor.
Embodiment 1:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the inculating crystal layer of ZnO:Al thereon, as target, the doping ratio of Al is the 2.0mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa, be that 99.99% argon gas is working gas with purity, operating air pressure maintains 1.2Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 60W, depositing time is 10min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 200nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Al film thereon.As target, the doping ratio of Al is 2.0mol% with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.2Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 100W, and depositing time is 30min, and the overall film thickness for preparing is 1.48 μ m.The surfaceness of prepared film is 20.1nm, and square resistance is 1.45 Ω/, and resistivity is 2.06 * 10
-4Ω cm, the visible light transmittance rate of this film more than 90%, 360nm place haze factor is 49.8%.
Fig. 4 is X-ray diffraction and the ADF shape appearance figure of prepared inculating crystal layer.By diagram as seen, prepared inculating crystal layer have along the high oriented growth in (002) crystal orientation, and compactness is good for receiving crystal structure.Fig. 5 adopts the surface topography SEM figure of the doping zinc-oxide film that magnetron sputtering method deposits for high directed at this and high fine and close inculating crystal layer, and Fig. 6 is the synoptic diagram of its light transmission and haze factor.The result can find out by its pattern, and its surface-texturing structure is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, the about 200nm of the bottom surface of single pyramidal structure height to the limit, the about 400nm of the maximum length of any point-to-point transmission in bottom surface.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has higher crystallinity.
Embodiment 2:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the inculating crystal layer of ZnO:Al earlier, as target, the doping ratio of Al is the 1.0mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa, be that 99.99% argon gas is working gas with purity, operating air pressure maintains 2.0Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 50W, depositing time is 5min, the inculating crystal layer inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 80nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Al film thereon.As target, the doping ratio of Al is the 2.0mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.2Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 140W, and depositing time is 20min, and the overall film thickness for preparing is 1.5 μ m.The surfaceness of prepared film is 40.2nm, and square resistance is 0.66 Ω/, and resistivity is 1.32 * 10
-4Ω cm, the visible light transmittance rate of this film more than 90%, 360nm place haze factor is 60.7%.
Fig. 7 is the surface topography SEM figure of the doping zinc-oxide film that adopts magnetron sputtering method at high directed and high fine and close inculating crystal layer and deposit, its cross-section morphology SEM figure and growth model are illustrated in Fig. 1 b, and cross-section morphology SEM figure and the growth model of the ZnO:Al film of no inculating crystal layer deposition is illustrated in Fig. 1 a as a comparison in the Comparative Examples.The result can find out by its pattern, and its surface-texturing structure is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, the about 400nm of the bottom surface of single pyramidal structure height to the limit, the about 800nm of the maximum length of any point-to-point transmission in bottom surface.Fig. 8 is the synoptic diagram of its light transmission and haze factor.Can be seen that by figure compare with Comparative Examples 1, this embodiment prepared film has extremely strong surface-texturing effect, haze factor enlarges markedly, and film has very high crystallinity.
Comparative Examples 2:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the prefabricated rete of ZnO:Al thereon.As target, the doping ratio of Al is the 1.25mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 2.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 0.5%), operating air pressure maintains 1.2Pa, adopt the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 80W, and depositing time is 40min, the prefabricated membrane inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 800nm.On prefabricated rete, adopt magnetron sputtering method deposition surface texturing ZnO:Al film again.As target, the doping ratio of Al is 2.0mol% with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is working gas with high-purity four 9 argon gas, and operating air pressure maintains 0.2Pa, adopts the room temperature sputter, and target and substrate distance are set to 7cm, adopts magnetically controlled DC sputtering, and sputtering power is 140W, and depositing time is 20min.Compare with embodiment 2, the deposition gained be thicker prefabricated rete but not inculating crystal layer, the texturing ZnO:Al film surface of last gained is microvoid structure, but not as the pyramid-like structure of embodiment 2.The surfaceness of prepared film is 11.1nm, and square resistance is 3.21 Ω/, and resistivity is 4.02 * 10
-4Ω cm, the visible light transmittance rate of this film about 85%, 360nm place haze factor is 15.3%.
Comparative Examples 3:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the prefabricated rete of ZnO:Al thereon.As target, the doping ratio of Al is the 3.0mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 2.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds a spot of H in addition
2And O
2(all account for total gas couette 0.5%), operating air pressure maintains 3.0Pa, underlayer temperature is 250 ℃, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 80W, and depositing time is 40min, the prefabricated membrane inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 650nm.On prefabricated rete, adopt magnetron sputtering method deposition surface texturing ZnO:Al film again.As target, the doping ratio of Al is 2.0mol% with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is working gas with high-purity four 9 argon gas, and operating air pressure maintains 0.2Pa, adopts the room temperature sputter, and target and substrate distance are set to 7cm, adopts magnetically controlled DC sputtering, and sputtering power is 140W, and depositing time is 20min.With Comparative Examples 2, compare with embodiment 2, this Comparative Examples has adopted higher power and long sputtering time in the first step, the deposition gained be thicker prefabricated rete but not inculating crystal layer, the texturing ZnO:Al film surface of last gained is microvoid structure, but not as the pyramid-like structure of embodiment 2.The surfaceness of prepared film is 10.7nm, and square resistance is 3.96 Ω/, and resistivity is 4.37 * 10
-4Ω cm, the visible light transmittance rate of this film about 85%, 360nm place haze factor is 13.6%.
Embodiment 3:
Be substrate with the simple glass, adopting sol-gel method to adopt concentration thereon is the Zn (CH of 1.0mol/L
3COO)
22H
2O and Ti (OR)
4Be raw material, the doping ratio of Ti is the 1.5mol% of Zn element, and the film that obtains after sol-gel method lifts makes the inculating crystal layer of ZnO:Ti behind 550 ℃ of annealing temperature 30min, and the inculating crystal layer of preparation is along the growth of (002) crystal face preferred orientation, and thickness is 20nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Ti film thereon.As target, the doping ratio of Ti is 5.0mol% with zno-based doped compound (ZnO:Ti), and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds a spot of O in addition
2And H
2Gas (O
2And H
2Account for respectively total gas couette 5% and 2%), operating air pressure maintains 1.2Pa, underlayer temperature is 90 ℃, target and substrate distance are set to 5cm, adopt rf magnetron sputtering, sputtering power is 90W, depositing time is 40min.The surfaceness of prepared film is 17.8nm, and square resistance is 6.3 Ω/, and resistivity is 3.9 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 25.7%, the thickness of prepared film is about 1.1 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly.
Embodiment 4:
Be substrate with the simple glass, adopt thermal evaporation to prepare the inculating crystal layer of ZnO:Sc at substrate earlier, little compacting block with ZnO:Sc is evaporation source, the doping of Sc is the 7.0mol% of Zn element, vaporization temperature is 450 ℃, and depositing time is 60min, and the distance of evaporation source and substrate is 7cm, the inculating crystal layer of preparation is along the growth of (002) crystal face preferred orientation, and thickness is 150nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Sc film thereon.As target, the doping ratio of Sc is the 0.25mol% of Zn element with zno-based doped compound (ZnO:Sc), and base vacuum is evacuated to 3.0 * 10
-4Pa is working gas with high-purity four 9 argon gas, and operating air pressure maintains 2.0Pa, adopts the room temperature sputter, and target and substrate distance are set to 8cm, adopts magnetically controlled DC sputtering, and sputtering power is 160W, and depositing time is 20min.The surfaceness of prepared film is 50.3nm, and square resistance is 1.33 Ω/, and resistivity is 1.68 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 68.2%, the total thickness of prepared film is about 1.0 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 5:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the inculating crystal layer of ZnO:Al at substrate earlier, as target, the doping ratio of Al is the 0.6mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa, be working gas with high-purity four 9 argon gas, operating air pressure maintains 1.8Pa, adopt the room temperature sputter, target and substrate distance are set to 9cm, adopt rf magnetron sputtering, sputtering power is 60W, depositing time is 15min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 200nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Al film thereon.As target, the doping ratio of Al is the 0.6mol% of Zn element with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.2Pa, adopts the room temperature sputter, and target and substrate distance are set to 7cm, the employing magnetically controlled DC sputtering, and sputtering power is 80W, depositing time is 40min.The surfaceness of prepared film is 15.1nm, and square resistance is 5.16 Ω/, and resistivity is 4.86 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 21.1%, the thickness of prepared film is about 1.16 μ m, compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 6:
Be substrate with the ceramic substrate, adopt Prepared by Sol Gel Method ZnO:(In at substrate earlier, inculating crystal layer B), adopting concentration is the Zn (CH of 0.5mol/L
3COO)
22H
2O and InNO
3, H
3BO
3Be raw material, be respectively 5.0mol% and 2.0mol% by the doping ratio of Zn In and B, the film after lifting makes ZnO:(In behind 650 ℃ of annealing temperature 40min, inculating crystal layer B), and inculating crystal layer is along the growth of (002) crystal face preferred orientation, and thickness is 120nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:(In, B) film thereon.With zno-based doped compound ZnO:(In, B) as target, be respectively 3.0mol% and 2.0mol% by the doping ratio of Zn In and B, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 2%), operating air pressure maintains 0.5Pa, underlayer temperature is 150 ℃, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, sputtering power is 170W, depositing time is 20min.The surfaceness of prepared film is 59.7nm, and square resistance is 0.79 Ω/, and resistivity is 1.46 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 72.8%, the thickness of prepared film is about 1.3 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 7:
Be substrate with the simple glass, adopt the inculating crystal layer of thermal evaporation preparation preparation ZnO:In earlier at substrate, little compacting block with ZnO:In is evaporation source, the doping of In is the 8.0mol% of Zn element, vaporization temperature is 450 ℃, and depositing time is 30min, and the distance of evaporation source and substrate is 4cm, inculating crystal layer is along the growth of (002) crystal face preferred orientation, and thickness is 250nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:In film thereon.As target, the doping ratio of In is 10mol% with zno-based doped compound (ZnO:In), and base vacuum is evacuated to 1.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 2%), operating air pressure maintains 3.0Pa, underlayer temperature is 150 ℃, target and substrate distance are set to 9cm, adopt magnetically controlled DC sputtering, sputtering power is 200W, depositing time is 10min.The surfaceness of prepared film is 56.3nm, and square resistance is 0.96 Ω/, and resistivity is 1.41 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 72.3%, the thickness of prepared film is about 1.60 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 8:
Be substrate with the silica glass, adopt pulsed laser deposition to prepare the inculating crystal layer of ZnO:Zr at substrate earlier, (wavelength is 248nm as light source to adopt the KrF excimer laser, single pulse energy 260mJ, pulse duration 25ns, frequency 5Hz), with high-purity ZnO powder and ZrO
2Be raw material, the doping of Zr is the 6.0mol% of Zn element, after ball milling, compacting, makes polycrystal target at 1000 ℃ of sintering, and underlayer temperature is 600 ℃, and depositing time is 20min, and the average laser energy density on the target is 6J/cm
2, inculating crystal layer is along the growth of (002) crystal face preferred orientation, and thickness is 120nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Zr film thereon.With zno-based doped compound purity be 99.99% (ZnO:Zr) as target, the doping ratio of Zr is 6.0mol%, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.3Pa, and underlayer temperature is 250 ℃, and target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, and sputtering power is 120W, and depositing time is 30min.The surfaceness of prepared film is 30.2nm, and square resistance is 3.54 Ω/, and resistivity is 3.28 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 52.9%, the overall film thickness for preparing is 1.2 μ m., to compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 9:
Be substrate with the simple glass, adopt thermal evaporation to prepare the inculating crystal layer of ZnO:Ga at substrate earlier, little compacting block with ZnO:Ga is evaporation source, the doping of Ga is the 1.0mol% of Zn element, vaporization temperature is 500 ℃, and depositing time is 40min, and the spacing of evaporation source and substrate is 7cm, the inculating crystal layer of preparation is along the growth of (002) crystal face preferred orientation, and thickness is 200nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Ga film thereon.As target, the doping ratio of Ga is 3.0mol% with zno-based doped compound (ZnO:Ga), and base vacuum is evacuated to 1.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds a spot of O in addition
2And H
2Gas (O
2And H
2Account for respectively total gas couette 1% and 10%), operating air pressure maintains 0.5Pa, underlayer temperature is 500 ℃, target and substrate distance are set to 5cm, adopt rf magnetron sputtering, sputtering power is 60W, depositing time is 60min.The surfaceness of prepared film is 23.6nm, and square resistance is 5.29 Ω/, and resistivity is 4.96 * 10
-4Ω cm, the visible light transmittance rate of this film is about 90%, 360nm place haze factor is 31.6%, preparation-obtained overall film thickness is 600nm.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 10:
Be substrate with the simple glass, adopt pulsed laser deposition to prepare ZnO:(Al, Ge at substrate earlier, Y) inculating crystal layer, (wavelength is 248nm, single pulse energy 260mJ as light source to adopt the KrF excimer laser, pulse duration 25ns, frequency 5Hz), with high-purity ZnO powder and Al
2O
3, GeO
2, Y
2O
3Be raw material, by Zn Al, the doping ratio of Ge and Y is respectively 2.0mol%, 0.25mol% and 5.0mol% after ball milling, compacting, make polycrystal target at 1200 ℃ of sintering, underlayer temperature is 50 ℃, and depositing time is 30min, and the average laser energy density on the target is 4J/cm
2, inculating crystal layer is along the growth of (002) crystal face preferred orientation, and thickness is 180nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:(Al thereon, Ge, Y) film.With zno-based doped compound ZnO:(Al, Ge, Y) as target, by Zn Al, the doping ratio of Ge and Y is respectively 2.0mol%, 0.25mol% and 5.0mol%, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.8Pa, and underlayer temperature is 150 ℃, and target and substrate distance are set to 6cm, adopt rf magnetron sputtering, and sputtering power is 120W, and depositing time is 25min.The surfaceness of prepared film is 45.6nm, and square resistance is 2.1 Ω/, and resistivity is 4.36 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 54.7%, the thickness of prepared film is about 1.2 μ m., to compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 11:
Be substrate with organosilicon/polyamide 6 imines film, adopt magnetron sputtering to prepare ZnO:(Pb at substrate earlier, Hf) inculating crystal layer, with zno-based doped compound ZnO:(Pb, Hf) as target, doping ratio by Zn Pb and Hf is respectively 3.0mol% and 2.0mol%, and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 0.5%), operating air pressure maintains 2.5Pa, adopts the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, and sputtering power is 30W, depositing time is 15min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 80nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:(Pb, Hf) film thereon.With zno-based doped compound ZnO:(Pb, Hf) as target, be respectively 1.5mol% and 1.0mol% by the doping ratio of Zn Pb and Hf, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 2.0%), operating air pressure maintains 0.2Pa, adopts the room temperature sputter, target and substrate distance are set to 7cm, the employing magnetically controlled DC sputtering, sputtering power is 180W, depositing time is 25min.The surfaceness of prepared film is 48.1nm, and square resistance is 2.21 Ω/, and resistivity is 2.03 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 75.2%, the thickness of prepared film is about 2.5 μ m, compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, haze factor enlarges markedly, and film has better electroconductibility.
Comparative Examples 4:
Be substrate with organosilicon/polyamide 6 imines film, adopt magnetron sputtering to prepare ZnO:(Pb at substrate earlier, Hf) inculating crystal layer, with zno-based doped compound ZnO:(Pb, Hf) as target, doping ratio by Zn Pb and Hf is respectively 3.0mol% and 2.0mol%, and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 0.5%), operating air pressure maintains 2.5Pa, adopts the room temperature sputter, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, and sputtering power is 30W, depositing time is 15min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 130nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:(Pb, Hf) film thereon.Base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 2.0%), operating air pressure maintains 0.3Pa, adopts the room temperature sputter, target and substrate distance are set to 7cm, the employing magnetically controlled DC sputtering, sputtering power is 120W, depositing time is 15min.The surfaceness of prepared film is 24.6nm, and square resistance is 6.22 Ω/, and resistivity is 5.69 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 38.5%, the thickness of prepared film is about 0.9 μ m, compare with Comparative Examples 1, this embodiment prepared film has significantly surface-texturing effect, haze factor increases to some extent, and film has better electroconductibility.But compare with embodiment 11, surfaceness and the haze factor of film all reduce, and the texturing effect is relatively poor.
Embodiment 12:
Be substrate with the simple glass, adopt magnetron sputtering method to prepare the crystal layer of receiving of ZnO:Al at substrate earlier, as target, namely doping ratio is 0mol% with unadulterated ZnO, and base vacuum is evacuated to 3.0 * 10
-4Pa, be that 99.99% argon gas is working gas with purity, operating air pressure maintains 2.0Pa, adopt the room temperature sputter, target and substrate distance are set to 5cm, adopt rf magnetron sputtering, sputtering power is 40W, depositing time is 8min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 50nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Al film thereon.As target, the doping ratio of Al is 0.25mol% with zno-based doped compound (ZnO:Al), and base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, and operating air pressure maintains 0.2Pa, adopts the room temperature sputter, and target and substrate distance are set to 7cm, the employing magnetically controlled DC sputtering, and sputtering power is 120W, depositing time is 25min.The surfaceness of prepared film is 34.3nm, and square resistance is 0.9 Ω/, and resistivity is 1.62 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 53.7%, the thickness of prepared film is about 1.15 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 13:
Be substrate with the silica glass, adopt magnetron sputtering to prepare ZnO:(Zr, inculating crystal layer Si) at substrate earlier, with zno-based doped compound ZnO:(Zr, Si) as target, be respectively 3mol% and 0.5mol% by the doping ratio of Zn Zr and Si, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 1.2%), operating air pressure maintains 3.0Pa, underlayer temperature is 500 ℃, target and substrate distance are set to 7cm, adopt magnetically controlled DC sputtering, and sputtering power is 30W, depositing time is 15min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 100nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:Zr film thereon.As target, be respectively 3mol% by the doping ratio of Zn Zr with zno-based doped compound ZnO:Zr, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 5.0%), operating air pressure maintains 2.5Pa, underlayer temperature is 500 ℃, target and substrate distance are set to 6cm, adopt magnetically controlled DC sputtering, sputtering power is 150W, depositing time is 20min.The surfaceness of prepared film is 48.6nm, and square resistance is 1.37 Ω/, and resistivity is 3.64 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 63.7%, the thickness of prepared film is about 1.9 μ m, compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 14:
Be substrate with the simple glass, adopt magnetron sputtering to prepare the inculating crystal layer of ZnO:In at substrate earlier, as target, be respectively 8mol% by the doping ratio of Zn In with zno-based doped compound ZnO:In, base vacuum is evacuated to 3.0 * 10
-4Pa, be that 99.99% argon gas is working gas with purity, operating air pressure maintains 2.2Pa, underlayer temperature is 350 ℃, and target and substrate distance are set to 8cm, adopts magnetically controlled DC sputtering, sputtering power is 50W, depositing time is 16min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 210nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO:In film thereon.As target, the doping ratio of In is 10mol% with zno-based doped compound (ZnO:In), and base vacuum is evacuated to 1.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 2%), operating air pressure maintains 3.0Pa, underlayer temperature is 150 ℃, target and substrate distance are set to 9cm, adopt magnetically controlled DC sputtering, sputtering power is 200W, depositing time is 25min.The surfaceness of prepared film is 59.7nm, and square resistance is 0.88 Ω/, and resistivity is 1.36 * 10
-4Ω cm, the visible light transmittance rate of this film greater than 90%, 360nm place haze factor is 80%, the thickness of prepared film is about 3.0 μ m.Compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, and haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 15:
Be substrate with the simple glass, adopt magnetron sputtering to prepare the inculating crystal layer of ZnO:Al at substrate earlier, as target, be respectively 3mol% by the doping ratio of Zn Al with zno-based doped compound ZnO:Al, base vacuum is evacuated to 3.0 * 10
-4Pa, be that 99.99% argon gas is working gas with purity, operating air pressure maintains 1.5Pa, underlayer temperature is 400 ℃, and target and substrate distance are set to 5cm, adopts rf magnetron sputtering, sputtering power is 40W, depositing time is 12min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 90nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO (Al, Y) film thereon.(Al Y) as target, is respectively 1.0mol% and 0.5mol% by the doping ratio of Zn Al and Y, and base vacuum is evacuated to 3.0 * 10 with zno-based doped compound ZnO
-4Pa is working gas with high-purity four 9 argon gas, and operating air pressure maintains 0.8Pa, and underlayer temperature is 200 ℃, and target and substrate distance are set to 5cm, adopts magnetically controlled DC sputtering, and sputtering power is 70W, and depositing time is 50min.The surfaceness of prepared film is 24.2nm, and square resistance is 4.76 Ω/, and resistivity is 4.234 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 34.8%, the thickness of prepared film is about 800nm, compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, haze factor enlarges markedly, and film has better electroconductibility.
Embodiment 16:
Be substrate with organosilicon/polyamide 6 imines film, adopt magnetron sputtering to prepare ZnO (In at substrate earlier, Ti, inculating crystal layer Sc) is with zno-based doped compound ZnO (In, Ti, Sc) as target, by Zn In, the doping ratio of Ti and Sc is respectively 7mol%, 1.5mol% and 0.5mol%, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 3.0%), operating air pressure maintains 2.8Pa, underlayer temperature is 150 ℃, target and substrate distance are set to 5cm, adopt magnetically controlled DC sputtering, and sputtering power is 20W, depositing time is 18min, the inculating crystal layer that deposits along (002) crystal face preferred orientation growth, thickness is 60nm.Be initial nucleus with inculating crystal layer again, adopt magnetron sputtering method deposition ZnO (In, Ti, Sc) film thereon.With zno-based doped compound ZnO (Sc) as target, by Zn In, the doping ratio of Ti and Sc is respectively 7mol% for In, Ti, 1.5mol% and 0.5mol%, base vacuum is evacuated to 3.0 * 10
-4Pa is that 99.99% argon gas is working gas with purity, feeds H in addition
2Gas (H
2Account for total gas couette 3.0%), operating air pressure maintains 1.6Pa, underlayer temperature is 150 ℃, target and substrate distance are set to 5cm, adopt magnetically controlled DC sputtering, sputtering power is 110W, depositing time is 30min.The surfaceness of prepared film is 30.8nm, and square resistance is 2.04 Ω/, and resistivity is 2.14 * 10
-4Ω cm, the visible light transmittance rate of this film about 90%, 360nm place haze factor is 49.7%, the thickness of prepared film is about 1.3 μ m, compare with Comparative Examples 1, this embodiment prepared film has tangible surface-texturing effect, haze factor enlarges markedly, and film has better electroconductibility.
The above only is preferred embodiment of the present invention, be not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if it is defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (28)
1. the auxiliary surface-texturing zinc oxide transparent conductive film of inculating crystal layer, comprise that one deck has fixedly zinc oxide inculating crystal layer or the doping zinc-oxide inculating crystal layer of crystallographic axis orientation, with should be fixedly in this inculating crystal layer upper edge the doping zinc-oxide tectum with surface-texturing structure of crystallographic axis oriented growth, wherein:
Doped element comprises one or more among B, Al, Ga, In, Sc, Y, Si, Ge, Sn, Pb, Ti, Zr and the Hf in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum;
The doped element total amount is the 0.25mol%～10mo1% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum;
The thickness of described inculating crystal layer is 20nm～250nm;
Described inculating crystal layer and tectal total thickness are 600nm～3.0 μ m;
Described surface-texturing structure is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, and the bottom surface of single pyramidal structure height to the limit is no more than 500nm,
The maximum length of any point-to-point transmission in bottom surface of described single pyramidal structure is no more than 1.0 μ m,
Described fixedly crystallographic axis is oriented to the c axle, and the scope of roughness of film is 15nm～60nm, and its 360nm haze factor is 20%～80%.
2. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 1, it is characterized in that the scope of roughness of film is 25nm～60nm, its 360nm haze factor is 30%～80%.
3. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 1, it is characterized in that the crystal formation of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer is zincblende lattce structure.
4. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 1, it is characterized in that the doped element total amount is the 0.25mol%～5mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum.
5. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 4, it is characterized in that the doped element total amount is the 0.5mol%～3.0mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum.
6. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 1, it is characterized in that the thickness of described inculating crystal layer is 80nm～150nm.
7. by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 1, it is characterized in that described inculating crystal layer and tectal total thickness are 800nm～1.8 μ m.
8. the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of inculating crystal layer comprises:
Have fixedly zinc oxide inculating crystal layer or the doping zinc-oxide inculating crystal layer of crystallographic axis orientation at substrate preparation one deck, and,
Fixedly crystallographic axis is orientated and prepares one deck doping zinc-oxide tectum with magnetron sputtering method in this zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer upper edge, wherein:
The doped element of described doping zinc-oxide comprises one or more among B, Al, Ga, In, Sc, Y, Si, Ge, Sn, Pb, Ti, Zr or the Hf;
The doped element total amount is the 0.25mol%～10mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum;
The thickness of the inculating crystal layer for preparing is 20nm～250nm;
The inculating crystal layer for preparing and tectal total thickness are 600nm～3.0 μ m, tectum has the surface-texturing structure, and the surface-texturing structure is for to be distributed in simultaneously on the same surface by a plurality of pyramidal structures, the bottom surface of single pyramidal structure height to the limit, be no more than 500nm
The maximum length of any point-to-point transmission in bottom surface of single pyramidal structure is no more than 1.0 μ m,
Described fixedly crystallographic axis is oriented to the c axle.
9. by the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8, it is characterized in that the crystal formation of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer is zincblende lattce structure.
10. press the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8, it is characterized in that the doped element total amount is the 0.25mol%～5mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum.
11. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 10, it is characterized in that the doped element total amount is the 0.5mol%～3.0mol% of Zn element in described doping zinc-oxide inculating crystal layer or the doping zinc-oxide tectum.
12. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8 is characterized in that the preparation method of described zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer comprises chemical deposition or physical deposition method.
13. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 12 is characterized in that, described chemical deposition comprises that sol-gel method lifts, sol-gel method spin coating or sol-gel method blade coating; Described physical deposition method comprises magnetron sputtering method or thermal evaporation sedimentation or pulsed laser deposition.
14. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 13 is characterized in that, the raw material that described sol-gel method lifts, sol-gel method spin coating or sol-gel method blade coating are selected for use is zinc acetate Zn (CH
3COO)
2.2H
2O, the concentration of Zn ion is 0.05mol/L～1.5mol/L, and annealing temperature is 400 ℃～800 ℃, and annealing time is 20min～90min.
15. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 13, it is characterized in that, the operating pressure of described magnetron sputtering method is 1Pa～3Pa, and depositing time is 5min～18min, and d.c. sputtering or radio-frequency sputtering power are 20W～60W.
16. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 15 is characterized in that the depositing time of described magnetron sputtering method is 5min～15min.
17. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 15 is characterized in that the d.c. sputtering of described magnetron sputtering method or radio-frequency sputtering power are 20W～55W.
18. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 15 is characterized in that the operating pressure of described magnetron sputtering method is 1.5Pa～2.5Pa.
19. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 17 is characterized in that the d.c. sputtering of described magnetron sputtering method or radio-frequency sputtering power are 30W～50W.
20. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 13, it is characterized in that, the vaporization temperature of described thermal evaporation is 350 ℃～650 ℃, and depositing time is 20min～60min, and the spacing of evaporation source and substrate is 4～9cm.
21. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 13, it is characterized in that, the underlayer temperature of described pulsed laser deposition is 20 ℃～700 ℃, and depositing time is 10min～40min, and the average laser energy density on the target is 2J/cm
2～10J/cm
2
22. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8, it is characterized in that, the tectal magnetron sputtering method of grow doping zinc oxide, comprise that with doping zinc-oxide body material be target, by magnetron sputtering with target as sputter on zinc oxide inculating crystal layer or doping zinc-oxide inculating crystal layer.
23. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 22, it is characterized in that described magnetron sputtering method comprises magnetically controlled DC sputtering, rf magnetron sputtering or magnetically controlled DC sputtering and rf magnetron sputtering mixing sputter.
24. press the preparation method of the auxiliary surface-texturing zinc oxide transparent conductive film of claim 22 or 23 described inculating crystal layers, it is characterized in that the operating pressure of described magnetron sputtering method is 0.1Pa～3Pa; Depositing time is 10min～60min; D.c. sputtering or radio-frequency sputtering power are 60W～200W.
25. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 24 is characterized in that the operating pressure of described magnetron sputtering method is 0.2Pa～1.5Pa; Depositing time is 20min～40min; D.c. sputtering or radio-frequency sputtering power are 100W～200W.
26. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8 is characterized in that the thickness of the doping zinc-oxide inculating crystal layer of preparation is 80nm～150nm.
27. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8 is characterized in that the tectal thickness of described doping zinc-oxide is 800nm～1.8 μ m.
28. the preparation method by the auxiliary surface-texturing zinc oxide transparent conductive film of the described inculating crystal layer of claim 8 is characterized in that described substrate is simple glass, silica glass, ceramic substrate or flexible organic polymer thin film substrate.
Priority Applications (1)
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| CN103397382B (en) * | 2013-04-01 | 2016-04-27 | 济南大学 | The preparation method of nanometic zinc oxide rod array film |
| CN103343335B (en) * | 2013-06-08 | 2016-03-23 | 徐东 | The preparation method of boron-doping zinc-oxide film |
| CN104037320B (en) * | 2014-05-28 | 2017-05-10 | 南京益得冠电子科技有限公司 | Large area manufacturing method for zinc oxide nano micro generators |
| CN107705873B (en) * | 2017-07-31 | 2019-04-16 | 北京大学深圳研究生院 | A kind of transparent conducting glass and its preparation method and application |
| CN107799415B (en) * | 2017-10-21 | 2020-04-03 | 河南大学 | Method for preparing boron-doped oxide dielectric film by chemical solution method |
| CN108103466A (en) * | 2017-12-21 | 2018-06-01 | 君泰创新（北京）科技有限公司 | The preparation method of high mobility transparent conductive oxide film |
| CN108396290B (en) * | 2018-02-24 | 2020-04-24 | 国家纳米科学中心 | TiZn alloy film and preparation method and application thereof |
| CN110129759B (en) * | 2019-06-27 | 2020-12-25 | 江阴恩特莱特镀膜科技有限公司 | Silicon-aluminum-zirconium target material for Low-E glass and preparation method thereof |
| CN113130742A (en) * | 2021-03-19 | 2021-07-16 | 厦门半导体工业技术研发有限公司 | Semiconductor integrated circuit device and method for manufacturing the same |
| CN114807854A (en) * | 2022-04-14 | 2022-07-29 | 华南理工大学 | Method for depositing alpha-alumina dielectric film on surface of silicon substrate |
| CN114775043A (en) * | 2022-04-20 | 2022-07-22 | 中国科学院半导体研究所 | Preparation method for improving film thickness uniformity |
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