CN102468347A - Solar cell device - Google Patents
Solar cell device Download PDFInfo
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- CN102468347A CN102468347A CN2010105321956A CN201010532195A CN102468347A CN 102468347 A CN102468347 A CN 102468347A CN 2010105321956 A CN2010105321956 A CN 2010105321956A CN 201010532195 A CN201010532195 A CN 201010532195A CN 102468347 A CN102468347 A CN 102468347A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a solar cell device. The solar cell device comprises a transparent substrate, a transparent conducting layer, a photovoltaic conversion element and an electrode layer, wherein the transparent conducting layer is arranged on the transparent substrate and comprises a lithium and fluorin co-doped tin oxide material and a plurality of polyhedron naked cores; the polyhedron naked cores have the polyhedron naked core distribution density between 60 percent and 95 percent; the photovoltaic conversion element is arranged on the transparent conducting layer; and the electrode layer is arranged on the photovoltaic conversion element.
Description
Technical field
The present invention relates to the making of solar battery apparatus, and be particularly related to a kind of solar battery apparatus and the manufacturing approach thereof of transparent conductive film with preferred light scattering properties.
Background technology
The application of transparent conductive film and demand constantly enlarge in recent years; It not only is applied to like display unit aspects such as the LCD (Liquid Crystal Display) in the two-d display panel (Fat Display Panel), electroluminescence display panel (Electro Luminescence Panel), plasma display (Plasma Display Panel), Field Emission Display (Field Emission Display), touch panels, and it also is applied to the application like other electronic product of solar cell.
Fig. 1 is a profile, has shown the application scenarios of the transparent conductive film in the known solar battery apparatus.As shown in Figure 1; Illustrating at this solar battery apparatus is that silicon film solar batteries (silicon thin film solar cell) installs 100; The tin oxide (fluorine doped tin oxide, FTO) main members such as the transparency conducting layer 104 of material, amorphous silicon membrane (amorphous silicon thin film) photo-electric conversion element 150 and electrode layer 112 that comprise the fluorine doping that is stacked in regular turn on the glass substrate 102.At this, amorphous silicon membrane photo-electric conversion element 150 comprises members such as piling up the p type amorphous silicon layer 106 that is arranged on the transparency conducting layer 104, intrinsic (intrinsic) amorphous silicon layer 108 and n type amorphous silicon layer 110 in regular turn.
Please with reference to Fig. 1; Though transparency conducting layer 104 adopts the stannic oxide materials of the fluorine doping with good light capture characteristic; Yet because the surface morphology of the stannic oxide materials that the fluorine that transparency conducting layer 104 is adopted mixes belongs to the plane kenel; So outside coming from glass substrate 102 as after incident light 180 incident of sunlight and penetrating glass substrate 102 and transparency conducting layer 104; Wherein more light component is with direct incident and penetrate amorphous silicon membrane photo-electric conversion element 150 but not for producing photovoltaic reaction within it, thereby has influenced the light utilization rate of amorphous silicon membrane photo-electric conversion element 150 for incident light 180.
Therefore, just need a kind of transparency conducting layer, to promote the light utilization rate of solar battery apparatus for incident light with preferred scattering nature.
Summary of the invention
In view of this, the invention provides a kind of solar battery apparatus, to solve above-mentioned known problem.
According to an embodiment, the invention provides a kind of solar battery apparatus, comprising: transparency carrier; Transparency conducting layer; Be arranged on this transparency carrier; Wherein this transparency conducting layer comprises lithium and fluorin-doped stannic oxide materials, and this transparency conducting layer comprises a plurality of polyhedron naked cores, and those polyhedron naked cores have the polyhedron naked core distribution density between 60-95%; Photo-electric conversion element is arranged on this transparency conducting layer; And electrode layer, be arranged on this photo-electric conversion element.
For let state on the present invention with other purpose, characteristic and advantage can be more obviously understandable, hereinafter is special lifts a preferred embodiment, and cooperates appended diagram, elaborates as follows
Description of drawings
Fig. 1 is a profile, has shown a kind of known solar cells device;
Fig. 2-5 has shown the manufacturing approach according to the solar battery apparatus of one embodiment of the invention;
Fig. 6-7 has shown the manufacturing approach according to the solar battery apparatus of another embodiment of the present invention;
Fig. 8 has shown the reflectance test result according to applied transparency conducting layer in the solar battery apparatus of an one embodiment of the invention and a comparative example;
Fig. 9 has shown the visible-light absorptivity test result according to applied transparency conducting layer in the solar battery apparatus of an one embodiment of the invention and a comparative example;
Figure 10 has shown the light reflectivity test result according to applied infrared light filter layer in the solar battery apparatus of an one embodiment of the invention and a comparative example;
Figure 11 has shown the light transmittance test result according to applied infrared light filter layer in the solar battery apparatus of an one embodiment of the invention and a comparative example;
Figure 12-13 has shown the manufacturing approach according to the solar battery apparatus of another embodiment of the present invention;
Figure 14 has shown the solar battery apparatus according to another embodiment of the present invention;
Figure 15 has shown the light transmittance test result according to applied infrared light filter layer in the solar battery apparatus of an one embodiment of the invention and a comparative example; And
Figure 16 has shown the light transmittance test result according to applied infrared light filter layer in the solar battery apparatus of an one embodiment of the invention and a comparative example.
Figure 17-19 has shown the measurement result of AFM.
Description of reference numerals
100～silicon film solar batteries device;
102～glass substrate;
The transparency conducting layer of 104～fluorine tin oxide material;
106～p type amorphous silicon layer;
108～intrinsic amorphous silicon layer;
110～n type amorphous silicon layer;
112～electrode layer;
150～photo-electric conversion element;
180～incident light;
200,300～non-crystal silicon solar cell device;
202～transparency carrier;
204,402～thin film deposition program;
206～transparency conducting layer;
206a～polyhedron naked core;
208～normal;
210～side edge surface;
212～p type amorphous silicon layer;
214～intrinsic amorphous silicon layer;
216～n type amorphous silicon layer;
218～photo-electric conversion element;
220～electrode layer;
250～incident light;
302～thin film deposition program;
304,404～infrared light filter layer;
406～anti-reflecting layer;
The surface of A, B～transparency carrier;
Normal in θ～polyhedron naked core and the angle between its each side edge surface;
The angle on the surface of ψ～side edge surface and transparency carrier;
The thickness of H～polyhedron naked core;
The bottom surface path length of W～polyhedron naked core.
Embodiment
Embodiments of the invention will and cooperate Fig. 2-7 to explain orally through hereinafter.
Please, show manufacturing approach according to the solar battery apparatus of one embodiment of the invention with reference to Fig. 2-5.
Please, transparency carrier 202 is provided at first, for example glass substrate, polymeric membrane plate base or flexible base plate with reference to Fig. 2.Then, implement thin film deposition program 204, on transparency carrier 202, to form transparent conductive film layer 206.Thin film deposition program 204 for example is chemical spray program or Atmospheric Chemistry synthesis program; It implements temperature approximately between 360～460 ℃; And the material of formed transparency conducting layer 206 for example is lithium and fluorin-doped tin oxide (lithium and fluorine co-doped tin oxide, Li-F:SnO
2), the lithium doping concentration in it approximately between 0.2～2.3at% and fluorine doping content approximately between 0.2～2.5at%, and preferably the lithium doping concentration in it approximately between 0.2～1.0at% and fluorine doping content approximately between 0.5～1.0at%.At this; Form by being formed at transparency carrier 202 lip-deep several polyhedron naked cores 206a through thin film deposition program 204 formed transparency conducting layers 206, thereby have rough on-plane surface kenel but not the plane kenel of the stannic oxide materials that known fluorine mixes.And these a little polyhedron naked core 206a in transparency conducting layer 206 have the polyhedron naked core distribution density between 60-95%, and wherein above-mentioned polyhedron naked core distribution density is defined as the ratio of polyhedron naked core 206a area occupied in the transparency conducting layer 206 interior unit ares.
Please, shown the amplification situation that constitutes the polyhedron naked core 206a of transparency conducting layer 206 with reference to the sketch map of Fig. 3.As shown in Figure 3; Have n side edge surface 210 and perpendicular to transparency carrier 202 normals to a surface 208 at this polyhedron naked core 206a; Wherein n is no less than 3; Have angle ψ between the surface of side edge surface 210 and transparency carrier 202, and normal 208 and its 210 of each side edge surface in the polyhedron naked core has the angle theta between 0 °～45 ° between 45 °～90 °.The bottom surface of polyhedron naked core 206a then has between 100～2000nm path length W, and has the thickness H between 300～1000nm.
In one embodiment; When adopting the chemical spray program to form transparency conducting layer 204, can will be mixed with like the carrier gas of air, oxygen, nitrogen and like Sn (OH) between the atomizer of 1.5KHz～2.6MHz or the accurate nozzle that has less than 10 microns openings like frequency of oscillation in utilization under 200 ℃～650 ℃ temperature
4, NH
4The size that mist produced of F, LiF, Li reacting gass such as (OH) forms on the transparency carrier 202 of heating between 5～15 microns droplet, and then has formed the transparency conducting layer of being made up of several polyhedron naked cores 204.
Because transparency conducting layer 206 is made up of several polyhedron naked cores 206a, thereby demonstrates nonplanar non-planar surface, so has approximately higher mist degree (haze level) between 20～60%.Help scattering by polyhedron naked core 206a in the transparency conducting layer 206 and be incident to incident light (not shown) in the solar battery apparatus to subsequent film, to promote the light component that gets into photo-electric conversion element in it and to promote its photoelectric conversion efficiency.In one embodiment; Measurement through BRDF (Bi-directional Reflectance Distribution Function) mensuration; The thin film deposition program 204 resulting transparency conducting layers of being made up of several polyhedron naked cores 206a 206 have the optical field distribution angle (α) between 40 °～80 °, are preferably 45 °～60 ° optical field distribution angle.
Please shine Fig. 4, then implement a thin film deposition program (not shown) on the transparency conducting layer 206 of structure shown in Figure 2, to form photo-electric conversion element 218.At this; It is an amorphous silicon p-i-n photoconductive structure that photo-electric conversion element 218 illustrates; But do not limit the present invention with this structure; Its also can adopt as dye-sensitized solar cells (Dye Sensitized Solar Cell, DSSC), the photoconductive structure of other form of nanocrystal silicon (Nanocrystalline silicon), multilayer storehouse (Tandem).In above-mentioned thin film deposition program, at first conformably form p type amorphous silicon layer 212 on transparency conducting layer 206; Then conformably form intrinsic (intrinsic; Promptly mix without admixture) amorphous silicon layer 214 on p type amorphous silicon layer 212, then conformably form a n type amorphous silicon layer 216 on intrinsic amorphous silicon layer 214.As shown in Figure 4; Because transparency conducting layer 206 has rough non-planar surface kenel, the surface that therefore conformably is formed at p type amorphous silicon layer 212, intrinsic amorphous silicon layer 214 and n type amorphous silicon layer 216 on the transparency conducting layer 206 also presents ups and downs non-planar surface kenel.The thin film deposition program can be accomplished in same technology board; And three retes that constitute photo-electric conversion element 218 can be accomplished the doping of specific electrical admixture when participating in the cintest and need not implement extra ion implantation step when thin film deposition, thereby can simplify the technology of photo-electric conversion element 218.At this, the thin film deposition program that forms photo-electric conversion element 218 for example is the reinforced chemical vapour deposition technique of plasma.
Please, then implement a thin film deposition program (not shown) with the smooth electrode layer 220 that forms on the photo-electric conversion element in structure shown in Figure 4 218 with reference to Fig. 5 with covering.At this, the thin film deposition program for example is a sputtering method, and the material of electrode layer 220 then for example is aluminium (Al), titanium (Ti), molybdenum (Mo) or silver (Ag).As shown in Figure 5, technology has so far just been accomplished the preparation of solar battery apparatus 200 substantially, comes from 250 extraneous of incident lights and can pass and arrive at photo-electric conversion element 218 places behind transparency carrier 202 and the transparency conducting layer 206 and give birth to the electricity reaction.
In the present embodiment; Solar battery apparatus 200 has been used and has been comprised the transparency conducting layer 206 that is made up of several polyhedron naked cores 206a; But employed polyhedron naked core gets into scattering and penetrate the incident light 250 of transparency carrier 202 in it; And then promote the light-inletting quantity that gets into photo-electric conversion element 218, thereby help to promote the light utilization efficiency of photo-electric conversion element 218 for incident light 250, the transparency conducting layer of this kind new structure can promote the element efficiency of solar battery apparatus.
Please, shown manufacturing approach according to the solar battery apparatus of another embodiment of the present invention with reference to Fig. 6-7.At this, present embodiment is resultant by the embodiment that revises shown in Fig. 2-5, therefore only describes the difference place between two embodiment at this, the identical member of same numeral representative in the accompanying drawings.
Please, transparency carrier 202 is provided at first, for example glass substrate, polymeric membrane plate base or flexible base plate with reference to Fig. 6.Then, implement thin film deposition program 302, on transparency carrier 202, to form infrared light filter layer 304.Thin film deposition program 302 for example is chemical spray program or Atmospheric Chemistry synthesis program; It implements temperature approximately between 200～650 ℃; And the material of formed infrared light filter layer 304 for example is lithium and fluorin-doped tin oxide (lithium and fluorine co-doped tin oxide; Li-F:SnO2), wherein lithium doping concentration approximately between 1.5～3.5at% and fluorine doping content approximately between 0.6～3.5at%, perhaps be zinc oxide (the fluorine and aluminum co-doped zinc oxide of fluorine and aluminium codope; F-Al:ZnO), wherein the fluorine doping content approximately between 0.1～2at% and aluminium doping content approximately between 1～5at%.In one embodiment; The thickness of formed infrared light filter layer 304 is approximately between 10～2000nm; It has the visible light mist degree that the infrared light that is higher than 70% visible light transmittance rate, is higher than 30% blocks rate and is less than 5%, thereby (penetrance of the light component between 1100～1800nm) is reduced to below 50% will to penetrate IR wavelength in the light of transparency carrier 202.At this, be formed at transparency carrier 202 surface through thin film deposition program 302 formed infrared light filter layers 304 and go up and have a flat surfaces kenel.
In one embodiment; When adopting the chemical spray program to form infrared light filter layer 304, can will be mixed with like the carrier gas of air, oxygen, nitrogen and like Sn (OH) between the atomizer of 1.5KHz～2.6MHz or the accurate nozzle that has less than 10 microns openings like frequency of oscillation in utilization under 200 ℃～650 ℃ temperature
4, NH
4The size that mist produced of F, LiF, Li reacting gass such as (OH) forms on the transparency carrier 202 of heating between 5～80 microns droplet, and then has formed infrared light filter layer 304.
Please with reference to Fig. 7; Then then can be with reference to manufacturing approach like Fig. 2～5 related embodiment; Continuation forms transparency conducting layer 206, photo-electric conversion element 218 and electrode layer 220 on infrared light filter layer 304 surfaces, and then has accomplished the making of solar battery apparatus 300.In the present embodiment; Solar battery apparatus 300 is except possessing the light utilization rate advantage of lifting photo-electric conversion element 218 for incident light 250 that is possessed like the solar battery apparatus in the previous embodiment 200, and the setting through infrared ray filter layer 304 is arrived at photo-electric conversion element 218 places with the light component of the incident light 250 mid-infrared light wavelength of avoiding getting into solar battery apparatus 300 in addition.So can avoid having absorbed the problem of the operating temperature that light component the caused lifting of the infrared band in the incident light 250, thereby guarantee that the photoelectric conversion efficiency of photo-electric conversion element 218 does not receive the influence of operating temperature and causes solar battery apparatus to give birth to the reduction of electrical efficiency because of photo-electric conversion element 218.The infrared light filter layer 304 of this kind new structure helps the stable operation degree of solar battery apparatus and the lifting in useful life.
Please, shown manufacturing approach according to the solar battery apparatus of further embodiment of this invention with reference to Figure 12-13.At this, present embodiment is resultant by the embodiment that revises shown in Fig. 2-5, therefore only describes the difference place between two embodiment at this, the identical member of same numeral representative in the accompanying drawings.
Please with reference to Figure 12, transparency carrier 202 is provided at first, for example glass substrate, polymeric membrane plate base or flexible base plate, this transparency carrier 202 have relative two surfaces A and B.Then implement thin film deposition program (not shown), on the surfaces A of transparency carrier 202, to form infrared light filter layer 404.Then implement thin film deposition program 402, on infrared light filter layer 404, to form anti-reflecting layer 406.
In one embodiment; The thin film deposition program that forms infrared light filter layer 404 for example is chemical spray program or Atmospheric Chemistry synthesis program; It implements temperature approximately between 340～650 ℃; And the material of formed infrared light filter layer 404 is through tin oxide (tin oxide) material that lithium, gallium, fluorine or antimony mixed, and wherein doping content is approximately between 0.6～3.5at%.And when infrared light filter layer 404 adopts the tin oxide that mixes through fluorine, then optionally more be doped with doping content approximately between the lithium atom of 1.5～3.5at%.In one embodiment; When adopting the chemical spray program to form infrared light filter layer 404, can will be mixed with like the carrier gas of air, oxygen, nitrogen and like Sn (OH) between the atomizer of 1.5KHz～2.6MHz or the accurate nozzle that has less than 10 microns openings like frequency of oscillation in utilization under 300～550 ℃ temperature
4, NH
4The mist of F, LiF, Li reacting gass such as (OH) forms on the transparency carrier 202 of heating with the size that the produces droplet between 5～80 microns, and then has formed infrared light filter layer 404.In one embodiment; The thickness of formed infrared light filter layer 404 is approximately between 100～600nm; And preferably approximately between 100～300nm; It has the visible light transmittance rate that is about 1.8～2.5 visible light refractive index (n), is higher than 80%, be higher than the visible light mist degree that 30% infrared light blocks rate and is less than 2%, thereby can (wavelength is reduced to below 40% between the penetrance of 1100～1800nm) light component with the IR wavelength in the light that gets into transparency carrier 202.At this, be formed at transparency carrier 202 lip-deep infrared ray filter layers 404 and have smooth surface morphology.
In one embodiment; The thin film deposition program 402 that forms anti-reflecting layer 406 for example is chemical spray program or Atmospheric Chemistry synthesis program; It implements temperature approximately between 100～250 ℃, and the material of formed anti-reflecting layer 406 for example is silicon dioxide or magnesium fluoride.In one embodiment; The thickness of formed anti-reflecting layer 406 is approximately between 100～180nm; And preferably approximately between 100～150nm; It has and is higher than 90% visible light transmittance rate, the visible light mist degree that is about 1.2～1.45 visible light refractive index (n) and is less than 2%; The setting of anti-reflecting layer 406 can't influence the infrared light light-filtering characteristic of infrared light filter layer 404 that is positioned at its below, and it can promote penetrating more than the spectral wavelength to 90% of the visible light that arrives at and penetrate transparency carrier 202 places.At this, the anti-reflecting layer 406 that is formed on the infrared light filter layer 406 through 402 of thin film deposition programs has smooth surface morphology.
Please with reference to Figure 13; Then then can be with reference to manufacturing approach like Fig. 2～5 related embodiment; Continuation forms element films such as transparency conducting layer 206, photo-electric conversion element 218 and electrode layer 220 in regular turn on another surperficial B of transparency carrier 202, and then has accomplished the making of solar battery apparatus 300.In the present embodiment; Solar battery apparatus 300 arrives at photo-electric conversion element 218 places through infrared ray filter layer 404 with the light component that reduces the infrared light wavelength in the incident light 250 that gets into solar battery apparatus 300 in addition except possessing the light utilization rate advantage of lifting photo-electric conversion element 218 for incident light 250 (being shown in Fig. 5) that is possessed like the solar battery apparatus in the previous embodiment 200.So can avoid having absorbed the problem of the operating temperature that light component the caused lifting of the infrared band in the incident light 250, thereby guarantee that the photoelectric conversion efficiency of photo-electric conversion element 218 does not receive the influence of operating temperature and causes solar battery apparatus to give birth to the reduction of electrical efficiency because of photo-electric conversion element 218.In addition, then can promote the light component of the visible wavelength in the incident light 250 (being shown in Fig. 5) that gets into solar battery apparatus 300 and arrive at photo-electric conversion element 218 places through the setting of anti-reflecting layer 406.Comprise that at this infrared light filter layer 404 and the NEW TYPE OF COMPOSITE film layer structure of anti-reflecting layer 406 help to promote the stable operation degree and the useful life of solar battery apparatus.
Please with reference to Figure 14; The NEW TYPE OF COMPOSITE rete that comprises infrared light filter layer 404 and anti-reflecting layer 406 shown in figure 13 in being applied to aforementioned solar battery apparatus 300; Also be applicable to its be integrated in known silicon film solar batteries as shown in Figure 1 (silicon thin film solar cell) device 100 in, improve the stable operation degree of solar battery apparatus 100 and the lifting in useful life thus.At this, present embodiment is resultant by revising enforcement situation as shown in Figure 1, therefore only describes the difference place between two embodiment at this, the identical member of same numeral representative in the accompanying drawings.
In the present embodiment; Infrared light filter layer 404 in the composite film and anti-reflecting layer 406 can be formed in regular turn on the glass substrate 102 (fluorine doped tinoxide is FTO) on another surface of main members such as the transparency conducting layer 104 of material, amorphous silicon membrane (amorphous silicon thin film) photo-electric conversion element 150 and electrode layer 112 with respect to being provided with the tin oxide that fluorine mixes.And employed glass substrate 102 does not limit with the substrate of glass material, and it also can be other transparency carrier of polymeric membrane plate base or flexible base plate.Ditto said, the setting through infrared ray filter layer 404 can reduce the light component that gets into solar battery apparatus 100 and arrive at the incident light 180 mid-infrared light wavelength at photo-electric conversion element 150 places.So can avoid having absorbed the problem of the operating temperature that light component the caused lifting of the infrared band in the incident light 180, thereby guarantee that the photoelectric conversion efficiency of photo-electric conversion element 150 does not receive the influence of operating temperature and causes solar battery apparatus to give birth to the reduction of electrical efficiency because of photo-electric conversion element 150.In addition, then can promote the light component of the visible wavelength in the incident light 180 that gets into solar battery apparatus 100 and arrive at photo-electric conversion element 150 places through the setting of anti-reflecting layer 406.The above-mentioned infrared light filter layer 404 and the NEW TYPE OF COMPOSITE rete of anti-reflecting layer 406 of comprising helps to promote the stable operation degree and the useful life of solar battery apparatus.
Embodiment:
Embodiment 1: the preparation of the transparency conducting layer of tool polyhedron naked core
At first, provide and contain 0.3 mole of SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.06 mole of codope
4Obtain a mixed aqueous solution behind the LiCl of F and 0.09 mole.Feed a miniature drop atomizer with air as carrier gas in addition; And through this miniature drop atomizer above-mentioned mixed aqueous solution is mixed the back with even air and directly be directed in through miniature drop atomizer through being heated to 400 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtained the SnO of the about 800nm of thickness
2: Li:F (Li-FTO) transparency conducting layer, it is made up of polyhedron naked core as shown in Figure 2 thereby has rough non-planar form surface, and warp is measured the path length of this polyhedron naked core between 200-300nm.At this, the doping that the doping of Li is about 0.3at% and F in the transparency conducting layer of resulting Li-FTO material is about 0.5at%.Warp is measured the optical field distribution angle of this transparency conducting layer between 45 °-55 °.Measurement through AFM (AFM); Polyhedron naked core in the transparency conducting layer of resulting Li-FTO material then has about 65% naked core distribution density, has then shown the surface topography distribution scenario of the transparency conducting layer that comprises the polyhedron naked core among Figure 17.
Embodiment 2: the preparation of the transparency conducting layer of tool polyhedron naked core
At first, provide and contain 0.3 mole of SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.06 mole of codope
4Obtain a mixed aqueous solution behind the LiCl of F and 0.12 mole.Feed a miniature drop atomizer with air as carrier gas in addition; And through this miniature drop atomizer above-mentioned mixed aqueous solution is mixed the back with even air and directly be directed in through miniature drop atomizer through being heated to 450 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtained the SnO of the about 850nm of thickness
2: Li:F (Li-FTO) (material) transparency conducting layer, it is made up of polyhedron naked core as shown in Figure 2 thereby has rough non-planar form surface, and warp is measured the path length of this polyhedron naked core between 500-600nm.At this, the doping that the doping of Li is about 0.5at% and F in the transparency conducting layer of resulting Li-FTO material is about 0.5at%.Warp is measured the optical field distribution angle of this transparency conducting layer between 65 °-75 °.Measurement through AFM (AFM); Polyhedron naked core in the transparency conducting layer of resulting Li-FTO material then has about 75% polyhedron naked core distribution density, has then shown the surface topography distribution scenario of the transparency conducting layer that comprises the polyhedron naked core among Figure 18.
Comparative example 1: the preparation of the transparency conducting layer of plane configuration
At first, provide and contain 0.3 mole of SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.045 mole of codope
4Obtain a mixed aqueous solution behind the F.Feed a miniature drop atomizer with air as carrier gas in addition; And through this miniature drop atomizer above-mentioned mixed aqueous solution is mixed the back with even air and directly be directed in through miniature drop atomizer once being heated to 360 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtained the SnO of the about 800nm of thickness
2: Li:F (Li-FTO) transparency conducting layer, it has the plane configuration surface of broadly similar in Fig. 1.At this, the doping of F is about 0.1at% in the transparency conducting layer of resulting Li-FTO material.Measurement through AFM (AFM); Polyhedron naked core in the transparency conducting layer of resulting Li-FTO material then has and is less than 30% polyhedron naked core distribution density; Thereby transparency conducting layer has the surface topography of almost plane form, then shown the surface topography distribution scenario of the transparency conducting layer of this plane configuration among Figure 19.
The light reflectivity test:
Fig. 8 shown embodiment 1 and 2 and comparative example 1 in the light reflectivity test result of transparency conducting layer.Measurement through reflection spectrometry (reflectance spectroscopy) can be learnt; Embodiment 1 and 2 and comparative example 1 in the light reflectivity of transparency conducting layer can significantly change along with the variation of the doping of Li element; Li element doping amount when being 0.3at% (embodiment 1) with 0.5at% (embodiment 2) incident light (wavelength is about 30% between the maximum of 1200～1800nm) reflectivity, but when the doping of Li is lower than 0.2at% its incident light (wavelength then is about 40-50% between 1200～1800nm) reflectivity.
The absorptivity test:
Fig. 9 shown embodiment 1 and 2 and comparative example 1 in the test result of absorptivity of transparency conducting layer.Measurement through absorption spectrometry (absorption spectroscopy) can be learnt; Embodiment 1 and 2 and comparative example 1 in the absorptivity of transparency conducting layer can significantly change along with the variation of the doping of Li element in it; The incident light of Li element doping amount when being 0.3at% (embodiment 1) with 0.5at% (embodiment 2) (wavelength is 30%-65% between 400～800nm) absorptivities, but when the doping of Li is lower than 0.2at% its incident light (wavelength is about 10-50% between 400～800nm) absorptivities.
Embodiment 3:
At first, provide and contain 0.5 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.35 mole of codope
4Behind the LiCl of F and 0.075 mole to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.Feed a miniature drop atomizer with air as carrier gas in addition, and will contain Sn (OH) through this miniature drop atomizer
4The aqueous solution and air to do the even back of mixing be to obtain a size under the 20L/min between 5～8 microns gas suspensoid air-flow through miniature drop atomizer at flow.Then, gas suspensoid air-flow directly is directed in through being heated to 400 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtains the transparent infrared light filter layer of the tin oxide master composition of the about 1000nm of thickness.At this, the doping of Li is about 1.5at% and the doping of F is about 1.0at% in the transparent infrared light filter layer of resulting tin oxide master composition.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Embodiment 4:
At first, provide and contain 0.5 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.35 mole of codope
4Behind the LiCl of F and 0.1 mole to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.In addition with air as carrier gas and and feed a miniature drop atomizer, and the aqueous solution that will contain Sn (OH) 4 through this miniature drop atomizer and air are done, and even to mix afterwards through miniature drop atomizer be to obtain a size under the 20L/min between 5～8 microns gas suspensoid air-flow at flow.Then, gas suspensoid air-flow directly is directed in through the test piece that is heated to 400 ℃ glass material does chemical vapour deposition (CVD), and then obtain the transparent infrared light filter layer of the tin oxide master composition of the about 1000nm of thickness.At this, the doping of Li is about 2.0at% and the doping of F is about 2.0at% in the transparent infrared light filter layer of resulting tin oxide master composition.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Embodiment 5:
At first, provide and contain 0.5 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution behind the LiCl of NH4F and 0.125 mole of 0.35 mole of codope to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.Feed a miniature drop atomizer with air as carrier gas in addition, and will contain Sn (OH) through this miniature drop atomizer
4The aqueous solution and air to do the even back of mixing be to obtain a size under the 20L/min between 5～8 microns gas suspensoid air-flow through miniature drop atomizer at flow.Then, gas suspensoid air-flow directly is directed in through being heated to 400 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtains the transparent infrared light filter layer of the tin oxide master composition of the about 1000nm of thickness.At this, the doping of Li is about 2.5at% and the doping of F is about 2.6at% in the transparent infrared light filter layer of resulting tin oxide master composition.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Comparative example 2:
At first, provide and contain 0.5 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and in this aqueous solution behind the NH4F of 0.35 mole of codope to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.Feed a miniature drop atomizer with air as carrier gas in addition, and will contain Sn (OH) through this miniature drop atomizer
4The aqueous solution and air to do the even back of mixing be to obtain size under the 20L/min between 5～8 microns gas suspensoid air-flow through miniature drop atomizer at flow.Then, gas suspensoid air-flow directly is directed in through being heated to 400 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtains the transparent red outside line secluding film of the tin oxide master composition of the about 1000nm of thickness.At this, the doping of Li is about 0at% and the doping of F is about 0.5at% in the transparent red outside line isolation layer of resulting tin oxide master composition.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
The light reflectivity test:
Figure 10 has shown the light reflectivity test result of the infrared light filter layer in embodiment 3-5 and the comparative example 2.Measurement through reflection spectrometry (reflectance spectroscopy) can be learnt; The incident light reflectivity of the infrared light filter layer in embodiment 3-5 and the comparative example 2 can significantly change along with the variation of the doping of elements such as Li, F; Incident light (ripple is longer than 1600nm) reflectivity when Li and F element doping amount are respectively 1.5at% and 1.0at% (embodiment 3), 2.0at% and 2.0at% (embodiment 4) and 2.5at% and 2.6at% (embodiment 5) be about 30%, 35% and 40% respectively, but its incident light (ripple is longer than 1600nm) reflectivity then is about 5% when the doping of Li and F is respectively 0at% and 0.5at% (comparative example 2).
The light transmittance test:
Figure 11 has shown the light transmittance test result of the infrared light filter layer in embodiment 3-5 and the comparative example 2.Measurement through penetrating spectroscopic methodology (transmission spectroscopy) can be learnt; The incident light penetrance of the infrared light filter layer in embodiment 3-5 and the comparative example 2 can significantly change along with the variation of the doping of elements such as Li, F; Incident light (ripple is longer than 1400nm) penetrance when Li and F element doping amount are respectively 1.5at% and 1.0at% (embodiment 3), 2.0at% and 2.0at% (embodiment 4) and 2.5at% and 2.6at% (embodiment 5) be about 30%, 20% and 10% respectively, but its incident light (ripple is longer than 1600nm) penetrance then is about 80% when the doping of Li and F is respectively 0at% and 0.5at% (comparative example 2).
Embodiment 6:
At first, provide and contain 0.5 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and 0.25 mole the NH of in this aqueous solution, mixing
4F is to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.Feed a miniature drop atomizer with air as carrier gas in addition, and will contain Sn (OH) through this miniature drop atomizer
4The aqueous solution and air to do the even back of mixing be to obtain size under the 10L/min between 10～80 microns gas suspensoid air-flow through miniature drop atomizer at flow.Then, gas suspensoid air-flow directly is directed in through being heated to 400 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtains the transparent infrared light filter layer of the tin oxide master composition that the fluorine of the about 500nm of thickness mixes.At this, the doping of fluorine is about 1.0at% in the transparent infrared light filter layer of resulting tin oxide master composition.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.Then, adopt the immersion plating method on formed transparent infrared light filter layer, to form the silica membrane that thickness is about 110 nanometers, it has and is about 1.3 refractive index (n).
Embodiment 7:
At first, provide and contain 0.3 mole SnCl
25H
2The aqueous solution of the tin metal salt of O, and 0.5 mole the NH4F of in this aqueous solution, mixing is to obtain containing Sn (OH)
4The aqueous solution, and this is contained Sn (OH)
4The aqueous solution place in the container.Feed a miniature drop atomizer with air as carrier gas in addition, and will contain Sn (OH) through this miniature drop atomizer
4The aqueous solution and air to do the even back of mixing be to obtain size under the 20L/min between 5～80 microns gas suspensoid air-flow through miniature drop atomizer at flow.Then, gas suspensoid air-flow directly is directed in through being heated to 380 ℃ the test piece of glass material forming chemical vapour deposition (CVD) above that, and then obtains the transparent infrared light filter layer of the tin oxide master composition that the fluorine of the about 130nm of thickness mixes.At this, the doping of the transparent infrared light filter layer F of resulting tin oxide master composition is about 1.5at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.Then, adopt the immersion plating method on formed transparent infrared light filter layer, to form the anti-reflecting layer that thickness is about the earth silicon material of 110 nanometers, it has and is about 1.3 refractive index (n).
Comparative example 3-4:
Implement situation with embodiment 6 and 7, only behind the transparent infrared light filter layer of the tin oxide master composition that the fluorine that forms about 500nm of thickness or 130nm mixes, form the anti-reflecting layer of earth silicon material no longer on it.
The light transmittance test:
Figure 15 has shown the light transmittance test result of the sample in embodiment 6 and the comparative example 3.Measurement through penetrating spectroscopic methodology (transmission spectroscopy) can be learnt; In sample like comparative example 3; Through the setting of infrared light filter layer, can show to be lower than 40% penetrance and to penetrate spectra part (for example in the 550nm place) at infrared spectrum part (for example in wavelength 1300nm place) and show and be about 80% penetrance at visible light.And in the sample like embodiment 6; Through the extra setting of anti-reflecting layer, can show almost constant penetrance (also being lower than 40%) and penetrate spectra part that to show than comparative example 3 be high penetrance (being about 90%) at infrared spectrum part (for example in wavelength 1300nm place) at visible light.
In addition, Figure 16 has then shown the light transmittance test result of the sample in embodiment 7 and the comparative example 4.Measurement through penetrating spectroscopic methodology (transmission spectroscopy) can be learnt; In sample like comparative example 4; Through the setting of infrared light filter layer, can show to be lower than 40% penetrance and to penetrate spectra part (for example in the 550nm place) at infrared spectrum part (for example in wavelength 1700nm place) and show and be about 88% penetrance at visible light.And in the sample like embodiment 7; Through the extra setting of anti-reflecting layer, can show almost constant penetrance (also being lower than 40%) and penetrate spectra part that to show than comparative example 4 be high penetrance (being about 95%) at infrared spectrum part (for example in wavelength 1700nm place) at visible light.
Though the present invention discloses as above with preferred embodiment; Right its is not in order to limit the present invention; Any those skilled in the art; Do not breaking away from the spirit and scope of the present invention, when can doing various changes and retouching, so protection scope of the present invention is as the criterion when looking appended the claim person of defining.
Claims (16)
1. solar battery apparatus comprises:
Transparency carrier;
Transparency conducting layer; Be arranged on this transparency carrier; Wherein this transparency conducting layer comprises lithium and fluorin-doped stannic oxide materials, and this transparency conducting layer comprises a plurality of polyhedron naked cores, and those polyhedron naked cores have the polyhedron naked core distribution density between 60-95%;
Photo-electric conversion element is arranged on this transparency conducting layer; And
Electrode layer is arranged on this photo-electric conversion element.
2. solar battery apparatus as claimed in claim 1, wherein the lithium doping amount in this lithium of this transparency conducting layer and the fluorin-doped stannic oxide materials between 0.2～2.3at% and fluorine doping between 0.2～2.5at%.
3. solar battery apparatus as claimed in claim 1, wherein the lithium doping amount in this lithium of this transparency conducting layer and the fluorin-doped stannic oxide materials between 0.2～1.0at% and fluorine doping between 0.5～1.0at%.
4. solar battery apparatus as claimed in claim 1, wherein this transparency conducting layer has the optical field distribution angle between 40 °～80 °.
5. solar battery apparatus as claimed in claim 1, wherein this transparency conducting layer has the optical field distribution angle between 45 °～60 °.
6. solar battery apparatus as claimed in claim 1, wherein this transparency conducting layer has the thickness between 300～1000nm.
7. solar battery apparatus as claimed in claim 1, wherein the bottom surface of those polyhedron naked cores in this transparency conducting layer has the path length between 100～2000nm.
8. solar battery apparatus as claimed in claim 1 also comprises the infrared light filter layer, is arranged between this transparency conducting layer and this transparency carrier.
9. solar battery apparatus as claimed in claim 8, wherein this infrared light filter layer comprises lithium and the fluorin-doped tin oxide or the zinc oxide of fluorine and aluminium codope.
10. solar battery apparatus as claimed in claim 8; Wherein this infrared light filter layer comprises lithium and fluorin-doped tin oxide, and the lithium doping concentration in this lithium and the fluorin-doped tin oxide approximately between 1.5～3.5at% and fluorine doping content approximately between 0.6～3.5at%.
11. solar battery apparatus as claimed in claim 1 also comprises infrared light filter layer and anti-reflecting layer, is arranged in regular turn on the surface of this transparency carrier with respect to this transparency conducting layer, wherein this anti-reflecting layer has the refractive index between 1.2-1.45.
12. solar battery apparatus as claimed in claim 11, wherein this infrared light filter layer comprises the tin oxide that mixes through lithium, gallium, fluorine or antimony.
13. solar battery apparatus as claimed in claim 11, wherein this anti-reflecting layer comprises silicon dioxide, magnesium fluoride.
14. solar battery apparatus as claimed in claim 11, wherein this infrared light filter layer has the thickness between 100～600nm.
15. solar battery apparatus as claimed in claim 11, wherein this anti-reflecting layer has the thickness between 100-180nm.
16. solar battery apparatus as claimed in claim 11, wherein this infrared light filter layer comprises the tin oxide that mixes through fluorine, and should more be doped with lithium atom through the tin oxide that fluorine mixes.
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| CN201010532195.6A CN102468347B (en) | 2010-11-02 | 2010-11-02 | Solar cell device |
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| CN201010532195.6A CN102468347B (en) | 2010-11-02 | 2010-11-02 | Solar cell device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103587422A (en) * | 2012-08-13 | 2014-02-19 | 王广武 | Car or boat with solar power generation ceiling |
| CN105511125A (en) * | 2015-12-30 | 2016-04-20 | 豪威半导体（上海）有限责任公司 | LCOS (Liquid Crystal on Silicon) display device and manufacturing method thereof |
| CN108444878A (en) * | 2018-04-20 | 2018-08-24 | 浙江大学 | A kind of portable aviation sprays the mist droplet deposition measurement of effectiveness device and method of operation |
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| US20060090790A1 (en) * | 2004-10-29 | 2006-05-04 | Mitsubishi Heavy Industries, Ltd. | Photoelectric conversion device |
| US20070074757A1 (en) * | 2005-10-04 | 2007-04-05 | Gurdian Industries Corp | Method of making solar cell/module with porous silica antireflective coating |
| US20090162697A1 (en) * | 2007-12-25 | 2009-06-25 | Industrial Technology Research Institute | Chlorine, fluorine and lithium co-doped transparent conductive films and methods for fabricating the same |
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| US20060090790A1 (en) * | 2004-10-29 | 2006-05-04 | Mitsubishi Heavy Industries, Ltd. | Photoelectric conversion device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103587422A (en) * | 2012-08-13 | 2014-02-19 | 王广武 | Car or boat with solar power generation ceiling |
| CN105511125A (en) * | 2015-12-30 | 2016-04-20 | 豪威半导体（上海）有限责任公司 | LCOS (Liquid Crystal on Silicon) display device and manufacturing method thereof |
| CN105511125B (en) * | 2015-12-30 | 2018-11-09 | 豪威半导体（上海）有限责任公司 | A kind of LCOS display devices and manufacturing method |
| CN108444878A (en) * | 2018-04-20 | 2018-08-24 | 浙江大学 | A kind of portable aviation sprays the mist droplet deposition measurement of effectiveness device and method of operation |
| CN108444878B (en) * | 2018-04-20 | 2024-03-26 | 浙江大学 | Device and method for measuring fog drop deposition effect of portable aviation spraying operation |
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| CN102468347B (en) | 2014-03-26 |
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