CN102652365B - There is silicon film solar batteries of improvement mist degree and preparation method thereof - Google Patents

Abstract

Improve the method for mist degree using chemical vapour phase deposition coating cloth method to improve the coating stack with top layer (18) and priming coat (16), including at least one following: raising precursor flow speed；Reduce carrier gas flow rate；Improve base material temperature；Improve water flow rate；Reduce exhaust-gas flow rate；With the thickness improved at least one of top layer or priming coat.

Description

There is silicon film solar batteries of improvement mist degree and preparation method thereof

Technical field

This patent disclosure relates generally to solaode, and in a particular implementation, relate to that there is improvement mist degree special The amorphous silicon thin-film solar cell of property.

Background technology

Conventional amorphous silicon thin-film solar cell typically comprises a glass baseplate, and it has transparent electric conductive oxidation Thing (TCO) contact layer and the amorphous silicon membrane active layer with p-n junction.The metal level at the back side plays the work of reflector and back contacts With.TCO has random surface to increase light scattering.In solar cells, light scattering or " mist degree " are used for capturing battery work Light in property region.In battery, the light of capture is the most, it is possible to the efficiency of acquisition is the highest.But, mist degree is not so large as to adversely shadow Ring the light transparency by TCO.Therefore, the capture of light is attempt to the important topic during efficiency improving solaode, and It is even more important in hull cell designs.But, in thin-film device, light capture is more difficult, because the thickness of layer ratio was previously Layer thickness in known single crystal device is much thinner.Along with film thickness reduces, they trend towards having substantial parallel table Face.Such parallel surfaces is not the most provided that significant light scattering.This is for by conventional chemical vapor deposition (CVD) Rubbing method deposition coating for the most obvious.Although the CVD rubbing method of routine yield with become present aspect to have advantage, but Conventional CVD deposition trends towards being formed the coating of the mist degree smooth even less than 0.5% on base material.Such lubricious allusion quotation It is not provided that the layer with the light scattering that be enough to significantly improve solar battery efficiency type.

Accordingly, it is desirable to provide the solaode of a kind of light scattering characteristic with improvement and manufacture this solaode Method, especially by CVD.

Summary of the invention

There is provided a kind of control such as to improve or reduce the method for mist degree of coating stack.Improve and there is top layer and priming coat The method of mist degree of coating stack include: deposition has the priming coat of surface roughness；It is deposited on by chemical gaseous phase On this priming coat, deposited top layer makes the surface roughness surface roughness more than described priming coat of described top layer.

The chemical vapour phase deposition coating cloth method raising of use has another of the mist degree of the coating stack of top layer and priming coat Method includes at least one following: improve precursor flow speed；Reduce carrier gas flow rate；Improve base material temperature；Improve current Dynamic speed；Reduce exhaust-gas flow rate；With the thickness improved at least one of top layer or priming coat.

Thin-film solar cells comprises the transparent base with at least one first type surface.First coating is formed at first type surface On Zhi Shaoyibufen, the first coating comprises one or more oxidations in the oxide of silicon, titanium, aluminum, stannum, zirconium and/or phosphorus Thing.Second coating be formed at the first coating at least some of on, the second coating comprise selected from Zn, Fe, Mn, Al, Ce, Sn, Sb, The oxidation of one or more of the alloy of Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si or In or two or more these materials One or more oxide materials in thing.

Accompanying drawing explanation

By following explanation and combine accompanying drawing and will obtain the complete understanding to the present invention.

Fig. 1 is the side cross-sectional, view (not in scale) of the solaode including inventive feature.

The explanation of preferred implementation

As used herein, space or direction term, such as "left", "right", " interior ", " outward ", " on ", D score etc. relate to this Time bright as shown in the drawing.However, it should be understood that the present invention can have various other orientation, therefore, this term should not be understood For limiting.Additionally, as used herein, all expression sizes used by specification and claims, physical features, processing ginseng The numeral of number, number of components, reaction condition etc. is interpreted as the most all being modified by term " about ".Therefore, unless phase Instead point out, the numerical value be given in description below and claims can according to the present invention seek obtain desired properties and Change.Nonetheless, and the scope to claim that is not intended to limit is suitable for doctrine of equivalents, and each numerical value should be according at least to note Record significant digits and by be suitable for commonly use rounding-off method explain.Additionally, all ranges disclosed herein is interpreted as containing The value of scope starting and ending and all any and whole subranges comprised in this range.Such as, described " 1 to 10 " Scope should be regarded as being included between minima 1 and maximum 10 any and all son of (and comprising this minima and maximum) Scope；That is, with minima 1 or more initial and with maximum 10 or all subranges of less end, such as 1 to 3.3,4.7 To 7.5,5.5 to 10 etc..Additionally, as used herein, term " ... upper formation ", " ... upper deposition " or " ... above provide " Represent and formed from the teeth outwards, deposit or provide, but need not directly contact this surface.Such as, the coating " at base material ... upper formation " Layer is not precluded between formed coating layer and described base material and there is one or more layers and have other of identical or different composition Dope layer or film.As used herein, term " polymer " " or " polymer " include oligomer, homopolymer, copolymer and ternary The polymer that copolymer, the monomer of the most two or more types or polymer are formed.Term " visual field " or " visible ray " Refer to that wave-length coverage is the electromagnetic radiation of 380nm to 760nm.Term " ultrared " or " infra-red radiation " refer to that wave-length coverage is more than The electromagnetic radiation of 760nm to 100000nm.Term " ultra-violet (UV) band " or " ultraviolet radiation " refer to that wave-length coverage is that 200nm is to being less than The electromagnetic energy of 380nm.Term " microwave region " or " microwave radiation " refer to that frequency range is 300 megahertzs of electromagnetism to 300 gigahertzs Radiation.Additionally, all documents mentioned above, such as, but not limited to, the patents and patent applications promulgated, should be regarded as it whole Content " is incorporated by reference into ".In the following discussion, refractive index value is that for reference wavelength is 550 nanometers (nm) A bit.Term " film " refers to the region with the coating of composition that is desired or that select." layer " comprises one or more layers " film "." coating " Or " coating stack " comprises one or more " layer ".

Exemplary solaode 10 including feature of present invention is shown in Figure 1.Solaode 10 comprise have to The base material 12 of a few first type surface 14.The first coating 16(priming coat of the present invention) it is formed at least some of of first type surface 14 On.Conductive oxide that second coating 18(is transparent or " TCO ") be formed at the first coating 16 at least some of on.Non-crystalline silicon Layer 20 be formed at the second coating 18 at least some of on.Metal or metal-containing layer 22 are formed at least of amorphous silicon layer 20 On Fen.

In the broad practice of the present invention, base material 12 can comprise any material requested with any desirable characteristics.Such as, Base material can be to visible transparent or translucent." transparent " refers to that transmission of visible light is more than 0% up to 100%.Or Person, base material 12 can be translucent." translucent " refers to allow electromagnetic energy (such as visible ray) by still making this energy Diffusion so that the object of observer's opposite side can not be high-visible.The example of the material being suitable for includes, but not limited to plastics base Material (such as acrylic polymer, such as polyacrylate；Polyalkyl methacrylate, such as poly-methyl methacrylate Ester, polyethyl methacrylate, polypropylmethacryla,es etc.；Polyurethane；Merlon；Polyalkylterephthalaor, example Such as polyethylene terephthalate (PET), PTT, polybutylene terephthalate (PBT) etc.；Containing poly- The polymer of siloxanes；Or for preparing the copolymer of these any monomer；Or their any mixture)；Glass baseplate； Or above-mentioned arbitrary mixture or combination.Such as, base material 12 can comprise the sodium carbonate-lime-silicate glass of routine, borosilicic acid Salt glass or lead glass.Glass can be pure glass." pure glass " refers to not dye or do not have the glass of coloring Glass.Or, glass can be dyeing or the glass otherwise coloured.Glass can be annealing or the glass of heat treatment Glass.As used herein, term " heat treatment " represents tempering or at least part of tempering.Glass can be any type, example Such as conventional float glass, and can be any composition with any optical property, described performance such as visible transmission Rate, ultraviolet light transmission, IR transmittance and/or the arbitrary value of total solar energy transmission." float glass " refers to pass through The glass that conventional float process is formed, wherein deposits to melted glass on the metal bath that melts and controllably cools down formed Float glass belt.Be not intended to the present invention, be suitable for base material glass example United States Patent (USP) 4746347,4792536, 5030593, described in 5030594,5240886,5385872 and 5393593.Can be used for glass non-limiting that the present invention implements Example includesGL-35^TM、 WithAll of all It is purchased from the PPG Industries Inc. of Pennsylvania Pittsburg.

Base material 12 can have the most required size, such as length, width, shape or thickness.Such as, base material 12 can To be plane, curved surface, or there is plane and curvature portion simultaneously.In a non-limiting embodiment, base material 12 Thickness can be 1mm to 10mm, such as 1mm to 5mm, such as 2mm to 4mm, such as 3mm to 4mm.

Base material 12 can have the high visible light transmissivity at reference wavelength 550 nanometer (nm) place." high visible transmission Rate " refer to that the transmission of visible light at 550nm, more than or equal to 85%, is greater than or equal to 87%, is greater than or is equal to 90%, it is greater than or equal to 91%, is greater than or equal to 92%.

In the practice of the present invention, the first coating 16(priming coat) may be used for impact, such as improve, the second of follow-up applying The roughness (" mist degree ") of coating 18, as described below.Have been found that and introduce slight mist degree or thick to priming coat 16 wittingly Rugosity (such as, surface roughness), this mist degree amplifies on the surface of the second coating 18.It is believed that this is because on priming coat 16 The crystal structure of two layer 18 does not mates.

The method that the roughness that improve first coating 16 and/or second coating 18 is described below.Non-limiting at one In embodiment, the first coating 16 comprises one or more oxidations in the oxide of silicon, titanium, aluminum, stannum, zirconium and/or phosphorus Thing.This oxide can exist with the most required ratio.Such as, the first coating 16 can comprise silicon dioxide.Or, first is coated with Layer 16 can comprise the mixture of silicon dioxide and titanium dioxide, and wherein silicon dioxide accounts for 0.1 percentage by weight (wt.%) extremely 99.9wt.% and titanium dioxide account for 99.9wt.% to 0.1wt.%.First coating 16 can be homogenizing coating.Or, the first coating 16 can be the gradient coating that the relative scale of the component of such as silicon dioxide or titanium dioxide changes along coating.Such as, first Coating 16 can be mainly silicon dioxide in the region adjacent with base material 12 surface, and in the perimeter of the first coating 16 (that is, away from the surface of base material 12) place is mainly titanium dioxide.Such as, the first coating 16 can be silicon dioxide, and thickness is 80nm to 90nm.

As it has been described above, the first coating 16 can comprise have selected from silicon, titanium, aluminum, stannum, zirconium and/or phosphorus element at least The mixture of two oxides.Such mixture includes, but not limited to titanium dioxide and phosphorous oxide；Silicon dioxide and oxidation Aluminum；Titanium dioxide and aluminium oxide；Silicon dioxide and phosphorous oxide；Titanium dioxide and phosphorous oxide；Silicon dioxide and stannum oxide, stannum oxide And phosphorous oxide, titanium dioxide and stannum oxide, aluminium oxide and stannum oxide, silicon dioxide and zirconium oxide；Titanium dioxide and zirconium oxide；Oxygen Change aluminum and zirconium oxide；Aluminium oxide and phosphorous oxide；Zirconium oxide and phosphorous oxide；Or the combination in any of above-mentioned material.The phase of each oxide Comparative example can be a kind of material and another material of 99.9wt% to 0.1wt% of any aequum, such as 0.1wt% to 99.9wt% Material.

Additionally, the first coating 16 can comprise at least three kinds of hopcalites, such as but not limited to, three kinds or more Plant the oxide with the element selected from silicon, titanium, aluminum, stannum, zirconium and/or phosphorus.Example includes, but not limited to comprise following mixing Compound: silicon dioxide, titanium dioxide and phosphorous oxide；Silicon dioxide, stannum oxide and phosphorous oxide；Silicon dioxide, titanium dioxide and oxygen Change aluminum；With silicon dioxide, titanium dioxide and zirconium oxide.Such as, the first coating 16 can comprise silicon dioxide and titanium dioxide with And selected from aluminium oxide, zirconium oxide and at least one other hopcalite of phosphorous oxide.The most such as, the first coating 16 is permissible Comprise silicon dioxide and stannum oxide and the mixing of at least one other oxide selected from aluminium oxide, zirconium oxide and phosphorous oxide Thing.The relative scale of oxide can be a kind of material of any aequum, such as 0.1wt.% to 99.9wt.%, 99.9wt.% To the second material of 0.1wt.%, and the third material of 0.1wt% to 99.9wt.%.

A kind of specific first coating 16 of the present invention includes the mixture of silicon dioxide, titanium dioxide and phosphorous oxide.Dioxy SiClx can account for 30 percents by volume (vol.%) to 80vol.%.Titanium dioxide can account for 5vol.% to 69vol.%.Phosphorous oxide can To account for 1vol.% to 15vol.%.

In another non-limiting embodiment, ground floor 16 can comprise anatase titanium dioxide.Have been found that and make Ground floor 16 with anatase titanium dioxide can improve the mist degree of the second layer 18.It is believed that this is because titania coatings 16 And on priming coat 16 formed the second layer 18 between crystallization do not mate.

First coating 16 can have the most required thickness, such as but not limited to, 10nm to 120nm, such as 30nm are extremely 100nm, such as 30nm to 90nm, such as 40nm to 90nm, such as 50nm to 90nm, such as 70nm to 90nm, such as 80nm are extremely 90nm。

In a non-limiting embodiment, the second coating 18 comprises at least one conductive oxide layer, such as, adulterate The oxide skin(coating) of matter.Such as, the second coating 18 can comprise one or more oxide materials, such as but not limited to, Zn, Fe, In the alloy of Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si or In or two or more these materials One or more oxides of one or more, such as zinc.Second coating 18 can also comprise one or more adulterants Material, such as but not limited to, F, In, Al, P and/or Sb.In a non-limiting embodiment, the second coating 18 is that fluorine is mixed Miscellaneous doped tin oxide coatings, wherein fluorine is measured less than 20wt.%, gross weight based on this precursor material present in coating precursor material Amount, such as less than 15wt.%, such as less than 13wt.%, such as less than 10wt.%, such as less than 5wt.%.Second coating 18 is permissible Be amorphous, crystallization or at least partly crystallization.

The thickness of the second coating 18 can be more than 200nm, is greater than 250nm, is greater than 350nm, is greater than 380nm, is greater than 400nm, is greater than 420nm, is greater than 500nm, is greater than 600nm.Non-limiting at one In embodiment, the second coating 18 comprises the stannum oxide of Fluorin doped and thickness as it has been described above, such as 350nm to 1000nm, example Such as 400nm to 800nm, such as 500nm to 700nm, such as 600nm to 700nm, such as 650nm.

Second coating 18(such as, the stannum oxide of Fluorin doped) surface resistivity can be less than 15 ohm/every square (Ω/), such as less than 14 Ω/, such as less than 13.5 Ω/, such as less than 13 Ω/, such as less than 12 Ω/, example As less than 11 Ω/, such as less than 10 Ω/.

The surface roughness (RMS) of the second coating 18 can be 5nm to 60nm, such as 5nm to 40nm, such as 5nm extremely 30nm, such as 10nm to 30nm, such as 10nm to 20nm, such as 10nm to 15nm, such as 11nm to 15nm.First coating 16 Surface roughness will be less than the surface roughness of the second coating 18.

The thickness of amorphous silicon layer 20 can be 200nm to 1000nm, such as 200nm to 800nm, such as 300nm extremely 500nm, such as 300nm to 400nm, such as 350nm.

Metal-containing layer 22 can be metal maybe can comprise one or more metal oxide materials.The metal oxygen being suitable for The example of compound material include, but not limited to Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si or The oxide of one or more, such as zinc in the alloy of In or two or more these materials.The thickness of metal-containing layer 22 Degree can be 50nm to 500nm, such as 50nm to 300nm, such as 50nm to 200nm, such as 100nm to 200nm, such as 150nm。

First coating 16 and/or the second coating 18 can by any conventional method base material 12 at least some of on shape Becoming, described conventional method is such as but not limited to, spray pyrolysis, chemical vapor deposition (CVD) or magnetron sputtered vacuum deposition (MSVD).Each layer can all be formed by same procedure, or different layers can be formed by distinct methods.In spray pyrolysis method In, will have one or more oxide precursor material (such as titanium dioxide and/or silicon dioxide and/or aluminium oxide and/or oxygen Change phosphorus and/or zirconic precursor material) the organic or compositions Han metal precursor be carried on suspension such as aqueous or non-aqueous Property solution in, and draw when base material is in and is high enough to cause precursor composition to decompose and forms the temperature of coating on base material Lead the surface of base material.Compositions can include one or more dopant materials.In CVD, precursor composition is carried on In carrier gas such as nitrogen, and it is directed on the base material of heating.In MSVD method, one or more cathode targets containing metal are being subtracted Pressure sputters with at deposited on substrates splash coating in inertia or oxygen-containing atmosphere.In coating process or hot radical can be added afterwards Material is so that the coating of sputtering crystallizes and forms coating.

In the non-limiting practice of one of the present invention, can be at one or many in conventional float glass band manufacturing process Individual position uses one or more CVD coating apparatus.For example, it is possible to float glass belt through tin bath time, it from tin bath out Afterwards, it enters before annealing furnace, it is through during annealing furnace or it uses CVD coating apparatus after annealing furnace is out.Cause The float glass belt of movement can be coated with for CVD, and bear the adverse circumstances relevant to manufacturing float glass belt, so CVD Method is particularly suitable on the float glass belt in melted tin bath depositing coating.United States Patent (USP) 4853257,4971843, 5536718,5464657,5714199 and 5599387 the CVD coating apparatus and method that may be used in present invention practice is described To be coated with float glass belt in melted tin bath.

In a non-limiting embodiment, one or more CVD coating machines may be located at the stannum on melted Xi Chi In bath.When float glass belt moves through tin bath, can the precursor composition of gasification be joined in carrier gas and be directed to band On upper surface.Precursor composition decomposes to form coating (such as, the first coating 16 and/or the second coating 18) on tape.Coating Compositions can band temperature less than 1300 °F (704 DEG C), such as less than 1250 °F (677 DEG C), such as less than 1200 °F (649 DEG C), such as less than 1190 °F (643 DEG C), such as less than 1150 °F (621 DEG C), such as less than 1130 °F (610 DEG C), such as The area deposition of 1190 °F to 1200 °F (643 DEG C to 649 DEG C) is to carrying.This have in deposition reduction surface resistivity the The stannum oxide of two coatings 18(such as Fluorin doped) time particularly useful because depositing temperature is the lowest, gained surface resistivity is the lowest.

Such as, in order to form the first coating 16 comprising silicon dioxide and titanium dioxide, said composition comprises dioxy simultaneously SiClx precursor and titanium dioxide precursor.One non-limitative example of silica precursor is tetraethylorthosilicise (TEOS).

The example of titanium dioxide precursor includes, but not limited to titanyl compound, low oxide or peroxide.One In individual embodiment, titania precursor material can include one or more Titanium alkoxides, such as but not limited to, methanol titanium, second Alcohol titanium, titanium propanolate, butanol titanium etc.；Or its isomer, such as isopropyl titanate, titanium tetraethoxide etc..It is suitable for showing of present invention practice The precursor material of example includes, but not limited to tetraisopropyl titanate (TPT).Or, titania precursor material can be tetrachloro Change titanium.The example of alumina precursor includes, but not limited to dimethyl aluminium isopropoxide (DMAP) and three aluminium secondary butylates (ATSB).Two Methyl isopropyl aluminium alcoholates can be by coming trimethyl aluminium and aluminum isopropylate. with the mixing of mol ratio 2:1 with under room temperature in an inert atmosphere Preparation.The example of phosphorous oxide precursor includes, but not limited to NSC 5284.The example of zirconium oxide precursor includes, but does not limits In, zirconium alkoxide.

First coating 16 with silicon dioxide and titanium dioxide combination had superiority than former combination of oxides.Such as, Low-index material such as silicon dioxide (at 550nm, refractive index is 1.5) and high-index material such as titanium dioxide (anatase titanium dioxide Titanium dioxide refractive index at 550nm is 2.48) combination make ground floor 16 refractive index can by change titanium dioxide The amount of silicon and titanium dioxide changes between two extreme values.This is for providing suppression color or iris aspect of performance for ground floor 16 Particularly useful.

But, the sedimentation rate of titanium dioxide is typically faster than the sedimentation rate of silicon dioxide.In typical deposition Under the conditions of, the amount of silicon dioxide is restricted to no more than about 50wt.% by this, and this again limit gained silicon dioxide/titanium dioxide afterwards The relatively low scope of the refractive index of titanium coating.Therefore, it can add adulterant material to silicon dioxide and titanium dioxide precursor compositions Expect to accelerate the deposition of silicon dioxide.Adulterant forms a part for gained oxide mixture, thus can select to provide The performance performance improved.For implement the example of the adulterant of the present invention include, but not limited in phosphorous, aluminum and zirconium a kind of or Multiple material is to form the oxide of these materials in gained coating.The example of phosphorous oxide precursor material includes tricresyl phosphite Ethyl ester.The example of alumina precursor material includes aluminium secondary butylate (ATSB) and dimethyl aluminium isopropoxide (DMAP).Zirconium oxide precursor Example include zirconium alkoxide.

In the specific non-limiting embodiment of one, chemical vapour phase deposition coating cloth method is used to apply first and/or the Two coatings.It has been determined that the mist degree of the coating of regulation deposition can be may be used for by the parameter of CVD rubbing method.Such as, in order to carry The mist degree of high specific coating, can change one or more following parameters according to following: (1) improves the flowing speed of precursor composition Rate；(2) flow rate of carrier gas is reduced；(3) base material temperature is improved；(4) water flow rate is improved；(5) waste gas flowing speed is reduced Rate；(6) thickness of coating, especially top layer is improved.

The following example is provided to illustrate each non-limiting aspect of the present invention.However, it should be understood that the present invention is not only restricted to this A little specific embodiments.

Embodiment 1

The explanation of this embodiment reduces the waste gas flowing impact on the mist degree of gained coating.

In this embodiment, in glass manufacturing process, use the chemical vapour phase deposition coating cloth machine deposition Fluorin doped of routine Doped tin oxide coatings (standard).The mist degree of standard specimen is less than 0.5%.Then, chemical vapour phase deposition coating cloth machine deposition fluorine is used to mix Miscellaneous doped tin oxide coatings, difference is to stop exhaust gas blower completely, only retains the waste gas flowing of ventilating system.From The mist degree that this sample records is 16.6%, is shown in table 1.It will be seen that the waste gas flowing reducing chemical vapour phase deposition coating cloth machine is notable Improve the mist degree of sample 1.

Table 1

Embodiment 2

In this embodiment, the various deposition parameters of regulation chemical gaseous phase sedimentary system are to determine the mist degree to gained coating Impact.Table 2 shows various deposition parameter and the performance recorded.

Table 2

As shown in table 2, reduction blower speed seems bigger than improving water flow rate for the impact of mist degree.

Embodiment 3

The explanation entrance carrier gas flow rate impact on the mist degree of gained coating of this embodiment.As shown in table 3, difference is used Entrance carrier gas flow rate prepare sample 5 and 6.By identical chemical flow rate, the belt speed of 5 identical inch/minute Degree, identical exhaust gas blower speed and identical water/MBTC ratio deposited samples 5 and 6.Unique parameter changed is entrance Carrier gas flow rate.As shown in table 3, mist degree (3.21%) ratio of the sample 5 with higher carrier gas flow rate has relatively low flowing The sample of speed is low.By reduce entrance flow rate about half, coating layer thickness only increases about 25%, and surface resistivity reduces about 6.6%, but mist degree carries three times higher.

Table 3

The atomic force microscope images of research sample 5 and 6, the surface ratio sample 5 of sample 6 is much coarser.As shown in table 4, Sample 6 more coarse than sample 5 about 29% to 40%.The scanning electron microscope image of sample 5 and 6 shows, sample 5 is than the crystalline substance of sample 6 Particle size is little.And according to X-ray diffraction result, sample 5 is also significantly (101) peak change compared with sample 6, and it is right to show Sample 6(101 in relatively haze) notable growth spatially.

Table 4

Those skilled in the art will readily appreciate that, can be to this under conditions of not going out the principle disclosed in described above Change is made in invention.Such as, the mist degree focusing primarily upon raising coating discussed above.It will be appreciated that by reverse above-mentioned technique also Mist degree can be reduced.Therefore, the particular implementation described in detail herein is only exemplary, rather than limits the present invention Scope, the scope of the present invention is provided complete scope by the claims below and its any and all equivalents.

Claims (21)

1. the method improving the mist degree of the coating stack with top layer and priming coat, including:

Deposition has surface roughness and the priming coat of the mixture comprising silicon dioxide, titanium dioxide and phosphorous oxide；With

It is deposited on deposited top layer on described priming coat so that the surface roughness of described top layer is more than the described end by chemical gaseous phase The surface roughness of coating, wherein said top layer comprise selected from Zn, Fe, Mn, Al, Ce, Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Conductive oxide and the described conductive oxide of Co, Cr, Si and In are adulterated by the adulterant selected from F, In, Al, P and Sb；

Described top layer at least some of on deposition of amorphous silicon films；With

Carry out selected from improving precursor flow speed, reducing carrier gas flow rate and reduce at least one coating of exhaust-gas flow rate Step is to improve the mist degree of coating stack.

2. the process of claim 1 wherein that the level of haze of described top layer is 5% to 30%.

3. the process of claim 1 wherein that described priming coat comprises anatase titanium dioxide；With

Wherein said top layer comprises the stannic oxide layer of Fluorin doped.

4. the process of claim 1 wherein that described priming coat comprises anatase titanium dioxide.

5. the process of claim 1 wherein that the transmission of visible light of coated article is for more than 80% and surface resistivity is low In 15 Ω/.

6. the method for claim 5, wherein said surface resistivity is less than 10 Ω/.

7. the method for claim 5, wherein said surface resistivity is 5 Ω/ to 9 Ω/.

8. the method for claim 1, including reducing exhaust-gas flow rate to obtain granular film deposition.

9. the process of claim 1 wherein that described priming coat comprises the mixture of silicon dioxide, titanium dioxide and phosphorous oxide, and Wherein silicon dioxide is in the range of 30vol.% to 80vol.%, and titanium dioxide is in the range of 5vol.% to 69vol.%, and oxygen Change phosphorus in the range of 1vol.% to 15vol.%.

10. the process of claim 1 wherein that conductive oxide is the stannum oxide of Fluorin doped.

11. the process of claim 1 wherein that coating step is to reduce exhaust-gas flow rate.

12. the process of claim 1 wherein that coating step is to reduce carrier gas flow rate.

13. the process of claim 1 wherein that coating step is to improve precursor flow speed.

The method of 14. claim 1, farther includes selected from the second coating step improving precursor flow speed.

The method of 15. claim 1, farther includes selected from improving precursor flow speed, reducing carrier gas flow rate, raising water Flow rate and the second coating step of reduction exhaust-gas flow rate.

16. the process of claim 1 wherein that at least one coating step is to reduce exhaust-gas flow rate；The method is wrapped further Including the second coating step and the 3rd coating step, this second coating step includes improving precursor flow speed, the 3rd coating step Suddenly include reducing carrier gas flow rate.

The method of 17. claim 1, further includes at least some of upper depositing metal-containing layers of amorphous silicon membrane.

The method of 18. claim 17, wherein said metal-containing layer includes metal-oxide.

19. the process of claim 1 wherein that the surface roughness of conductive oxide layer is 5nm to 60nm.

20. 1 kinds of thin-film solar cells, comprise:

There is the transparent base of at least one first type surface；

Be formed at described first type surface at least some of on the first coating, this first coating has surface roughness and comprise two The mixture of silicon oxide, titanium dioxide and phosphorous oxide；

Be formed at the first coating at least some of on the second coating, this second coating comprise selected from Zn, Fe, Mn, Al, Ce, The conduction of the alloy of the material of Sn, Sb, Hf, Zr, Ni, Zn, Bi, Ti, Co, Cr, Si, In and two or more these materials Oxide, wherein the second coating is adulterated by the adulterant selected from F, In, Al, P and Sb and the surface roughness of the second coating is more than The surface roughness of the first coating,

Amorphous silicon membrane on conductive oxide layer is at least some of；

Wherein carry out selected from improving at least one coating step of precursor flow speed to improve the mist degree of coating stack.

The solaode of 21. claim 20, wherein the second coating comprises the stannum oxide of Fluorin doped.