CN102468347B - Solar cell device - Google Patents
Solar cell device Download PDFInfo
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- CN102468347B CN102468347B CN201010532195.6A CN201010532195A CN102468347B CN 102468347 B CN102468347 B CN 102468347B CN 201010532195 A CN201010532195 A CN 201010532195A CN 102468347 B CN102468347 B CN 102468347B
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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
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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 manufacture method thereof of the transparent conductive film with preferred light scattering properties.
Background technology
The application of transparent conductive film and demand constantly expand in recent years, it is not only applied to as display unit aspects such as the liquid crystal display (Liquid Crystal Display) in 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 is also applied to as the application of other electronic product of solar cell.
Fig. 1 is a profile, has shown the application scenarios of the transparent conductive film in known solar battery apparatus.As shown in Figure 1, at this solar battery apparatus, illustrate as silicon film solar batteries (silicon thin film solar cell) device 100, the main members such as transparency conducting layer 104, amorphous silicon membrane (amorphous silicon thin film) photo-electric conversion element 150 and electrode layer 112 that comprise tin oxide (fluorine doped tin oxide, the FTO) material of the fluorine doping being sequentially stacked on glass substrate 102.At this, amorphous silicon membrane photo-electric conversion element 150 comprises the sequentially stacking members such as p-type amorphous silicon layer 106, intrinsic (intrinsic) amorphous silicon layer 108 and N-shaped amorphous silicon layer 110 that are arranged on transparency conducting layer 104.
Please refer to Fig. 1, although transparency conducting layer 104 adopts the stannic oxide materials of the fluorine doping with good light capture characteristic, yet the surface morphology of the stannic oxide materials that the fluorine adopting due to transparency conducting layer 104 adulterates belongs to plane kenel, therefore outside coming from glass substrate 102 as after incident light 180 incident of sunlight penetrating glass substrate 102 and transparency conducting layer 104, wherein more light component is by direct incident and penetrate amorphous silicon membrane photo-electric conversion element 150 but not for producing photovoltaic reaction within it, thereby affected 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 with preferred scattering nature, to promote solar battery apparatus for the light utilization rate of incident light.
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.
In order to allow on the present invention, to state with other object, feature and advantage and can become apparent, a preferred embodiment cited below particularly, and coordinate appended diagram, be described in detail below
Accompanying drawing explanation
Fig. 1 is a profile, has shown a kind of known solar cells device;
Fig. 2-5 have shown the manufacture method according to the solar battery apparatus of one embodiment of the invention;
Fig. 6-7 have shown the manufacture method 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 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 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 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 one embodiment of the invention and a comparative example;
Figure 12-13 have shown the manufacture method 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 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 one embodiment of the invention and a comparative example.
Figure 17-19 have shown the measurement result of atomic force microscope.
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-shaped 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-shaped 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;
Angle between the normal in θ～polyhedron naked core and its each side edge surface;
The surperficial angle 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 be by below and coordinate Fig. 2-7 to be explained orally.
Please refer to Fig. 2-5, show the manufacture method according to the solar battery apparatus of one embodiment of the invention.
Please refer to Fig. 2, first transparency carrier 202 is provided, for example glass substrate, polymeric membrane plate base or flexible base plate.Then, implement thin film deposition program 204, to form transparent conductive film layer 206 on transparency carrier 202.Thin film deposition program 204 is for example chemical spray program or Atmospheric Chemistry synthesis program, it implements temperature approximately between 360～460 ℃, and the material of formed transparency conducting layer 206 is for example 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, by the formed transparency conducting layer 206 of thin film deposition program 204, by being formed at the lip-deep several polyhedron naked core 206a of transparency carrier 202, formed, thereby there is rough on-plane surface kenel but not the plane kenel of the stannic oxide materials that known fluorine adulterates.And these a little polyhedron naked core 206a in transparency conducting layer 206 have the polyhedron naked core distribution density between 60-95%, wherein above-mentioned polyhedron naked core distribution density is defined as the ratio of polyhedron naked core 206a area occupied in the interior unit are of transparency conducting layer 206.
Please refer to the schematic diagram of Fig. 3, shown the amplification situation that forms the polyhedron naked core 206a of transparency conducting layer 206.As shown in Figure 3, at this polyhedron naked core 206a, there is n side edge surface 210 and perpendicular to transparency carrier 202 normals to a surface 208, wherein n is no less than 3, between the surface of side edge surface 210 and transparency carrier 202, there is the angle ψ between 45 °～90 °, and the normal in polyhedron naked core 208 and its 210 of each side edge surface has the angle theta between 0 °～45 °.The bottom surface of polyhedron naked core 206a has between 100～2000nm path length W, and has the thickness H between 300～1000nm.
In one embodiment, when adopting chemical spray program to form transparency conducting layer 204, can at the temperature between 200 ℃～650 ℃, utilize if frequency of oscillation is between the atomizer of 1.5KHz～2.6MHz or have the accurate nozzle that is less than 10 microns of openings and will be mixed with as the carrier gas of air, oxygen, nitrogen and as Sn (OH)
4, NH
4the size that the mist of the reacting gass such as F, LiF, Li (OH) produces forms on the transparency carrier 202 of heating between the droplet of 5～15 microns, and then has formed the transparency conducting layer 204 being comprised of several polyhedron naked cores.
Therefore because transparency conducting layer 206 is comprised of several polyhedron naked core 206a, thereby present nonplanar non-planar surface, there is approximately the higher mist degree (haze level) between 20～60%.By the interior polyhedron naked core of transparency conducting layer 206 206a, be conducive to scattering and be incident to incident light (not shown) in solar battery apparatus to subsequent film, to promote, enter the light component of photo-electric conversion element in it and promote its photoelectric conversion efficiency.In one embodiment, by the measurement of BRDF (Bi-directional Reflectance Distribution Function) mensuration, the resulting transparency conducting layer 206 being comprised of several polyhedron naked core 206a of thin film deposition program 204 has the optical field distribution angle (α) between 40 °～80 °, is preferably the optical field distribution angle of 45 °～60 °.
Please shine Fig. 4, then implement a thin film deposition program (not shown) to form photo-electric conversion element 218 on the transparency conducting layer 206 in structure shown in Fig. 2.At this, it is an amorphous silicon p-i-n photoconductive structure that photo-electric conversion element 218 illustrates, but with this structure, be not limited the present invention, it also can adopt as the photoconductive structure of other form of dye-sensitized solar cells (Dye Sensitized Solar Cell, DSSC), nanocrystal silicon (Nanocrystalline silicon), Multilayer stack (Tandem).In above-mentioned thin film deposition program, first conformably form p-type amorphous silicon layer 212 on transparency conducting layer 206, then conformably form intrinsic (intrinsic, without admixture doping) amorphous silicon layer 214 on p-type amorphous silicon layer 212, then conformably form a N-shaped amorphous silicon layer 216 in intrinsic amorphous silicon layer 214.As shown in Figure 4, because transparency conducting layer 206 has rough non-planar surface kenel, the surface that is therefore conformably formed at p-type amorphous silicon layer 212, intrinsic amorphous silicon layer 214 and N-shaped amorphous silicon layer 216 on transparency conducting layer 206 also presents ups and downs non-planar surface kenel.Thin film deposition program can complete in same technique board, and three retes that form photo-electric conversion element 218 can complete the doping of specific electrical admixture when participating in the cintest and not need to implement extra Implantation step when thin film deposition, thereby can simplify the technique of photo-electric conversion element 218.At this, the thin film deposition program that forms photo-electric conversion element 218 is for example the reinforced chemical vapour deposition technique of plasma.
Please refer to Fig. 5, then implement a thin film deposition program (not shown) and form electrode layer 220 with smooth covering on the photo-electric conversion element 218 in structure shown in Fig. 4.At this, thin film deposition program is for example sputtering method, and the material of electrode layer 220 is for example aluminium (Al), titanium (Ti), molybdenum (Mo) or silver (Ag).As shown in Figure 5, technique so far, has just completed the preparation of solar battery apparatus 200 substantially, come from 250 of extraneous incident lights can through transparency carrier 202 with after transparency conducting layer 206, arrive at photo-electric conversion element 218 places and give birth to electric reaction.
In the present embodiment, solar battery apparatus 200 has been applied and has been comprised the transparency conducting layer 206 consisting of several polyhedron naked core 206a, the polyhedron naked core using in it can scattering enters and penetrates the incident light 250 of transparency carrier 202, and then lifting enters the light-inletting quantity of photo-electric conversion element 218, thereby contributing to promote photo-electric conversion element 218 for the light utilization efficiency of incident light 250, the transparency conducting layer of this kind of new structure can promote the element efficiency of solar battery apparatus.
Please refer to Fig. 6-7, shown the manufacture method according to the solar battery apparatus of another embodiment of the present invention.At this, the present embodiment is resulting by the embodiment revising as shown in Figure 2-5, therefore at this, only describes the difference place between two embodiment, and same numeral represents identical member in the accompanying drawings.
Please refer to Fig. 6, first transparency carrier 202 is provided, for example glass substrate, polymeric membrane plate base or flexible base plate.Then, implement thin film deposition program 302, to form infrared light filter layer 304 on transparency carrier 202.Thin film deposition program 302 is for example 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 is for example 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%, or be zinc oxide (the fluorine and aluminum co-doped zinc oxide of fluorine and aluminium codope, F-Al:ZnO), wherein 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 ray mist degree that visible light transmittance rate, the infrared light higher than 30% higher than 70% block rate and be less than 5%, thereby the penetrance that penetrates the light component of the Infrared wavelength (between 1100～1800nm) in the light of transparency carrier 202 is reduced to below 50%.At this, by the formed infrared light filter layer 304 of thin film deposition program 302, be formed at transparency carrier 202 surfaces above and there is flat surfaces kenel.
In one embodiment, when adopting chemical spray program to form infrared light filter layer 304, can at the temperature between 200 ℃～650 ℃, utilize if frequency of oscillation is between the atomizer of 1.5KHz～2.6MHz or have the accurate nozzle that is less than 10 microns of openings and will be mixed with as the carrier gas of air, oxygen, nitrogen and as Sn (OH)
4, NH
4the size that the mist of the reacting gass such as F, LiF, Li (OH) produces forms on the transparency carrier 202 of heating between the droplet of 5～80 microns, and then has formed infrared light filter layer 304.
Please refer to Fig. 7, then can be with reference to as the manufacture method of 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 completed the making of solar battery apparatus 300.In the present embodiment, solar battery apparatus 300 is except possessing the lifting photo-electric conversion element 218 that possessed as the solar battery apparatus 200 in the previous embodiment light utilization rate advantage for incident light 250, and the setting by infrared ray filter layer 304 is arrived at photo-electric conversion element 218 places to avoid entering the light component of the incident light 250 mid-infrared light wavelength of solar battery apparatus 300 in addition.So can avoid because photo-electric conversion element 218 has absorbed the problem that operating temperature that the light component of the infrared band in incident light 250 causes promotes, thereby the photoelectric conversion efficiency of having guaranteed photo-electric conversion element 218 is not subject to the impact of operating temperature and causes the reduction of the raw electrical efficiency of solar battery apparatus.The infrared light filter layer 304 of this kind of new structure contributes to the stable operation degree of solar battery apparatus and the lifting in useful life.
Please refer to Figure 12-13, shown the manufacture method according to the solar battery apparatus of further embodiment of this invention.At this, the present embodiment is resulting by the embodiment revising as shown in Figure 2-5, therefore at this, only describes the difference place between two embodiment, and same numeral represents identical member in the accompanying drawings.
Please refer to Figure 12, first transparency carrier 202 is provided, for example glass substrate, polymeric membrane plate base or flexible base plate, this transparency carrier 202 has relative two surface A and B.Then implement thin film deposition program (not shown), to form infrared light filter layer 404 in the surface A at transparency carrier 202.Then implement thin film deposition program 402, to form anti-reflecting layer 406 on infrared light filter layer 404.
In one embodiment, the thin film deposition program that forms infrared light filter layer 404 is for example chemical spray program or Atmospheric Chemistry synthesis program, it implements temperature approximately between 340～650 ℃, and tin oxide (tin oxide) material of the material of formed infrared light filter layer 404 for adulterating through lithium, gallium, fluorine or antimony, wherein doping content is approximately between 0.6～3.5at%.And when infrared light filter layer 404 adopts the tin oxide through fluorine doping, optionally more doped with doping content approximately between the lithium atom of 1.5～3.5at%.In one embodiment, when adopting chemical spray program to form infrared light filter layer 404, can at the temperature between 300～550 ℃, utilize if frequency of oscillation is between the atomizer of 1.5KHz～2.6MHz or have the accurate nozzle that is less than 10 microns of openings and will be mixed with as the carrier gas of air, oxygen, nitrogen and as Sn (OH)
4, NH
4the mist of the reacting gass such as F, LiF, Li (OH), the droplet with the size that produces between 5～80 microns forms on the transparency carrier 202 of heating, 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 and is about the visible ray mist degree that 1.8～2.5 visible ray refractive index (n), the visible light transmittance rate higher than 80%, the infrared light higher than 30% block rate and be less than 2%, thereby the penetrance that enters the light component of the Infrared wavelength (wavelength is between 1100～1800nm) in the light of transparency carrier 202 can be reduced to below 40%.At this, be formed at the lip-deep infrared ray filter layer 404 of transparency carrier 202 and there is smooth surface morphology.
In one embodiment, the thin film deposition program 402 that forms anti-reflecting layer 406 is for example chemical spray program or Atmospheric Chemistry synthesis program, it implements temperature approximately between 100～250 ℃, and the material of formed anti-reflecting layer 406 is for example 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 the visible light transmittance rate higher than 90%, the visible ray mist degree that is about 1.2～1.45 visible ray refractive index (n) and is less than 2%, the setting of anti-reflecting layer 406 can't affect the infrared light light-filtering characteristic of infrared light filter layer 404 that is positioned at its below, and more than it can promote the penetrating light spectrum wavelength to 90% of the visible ray that arrives at and penetrate transparency carrier 202 places.At this, the anti-reflecting layer 406 being formed on infrared light filter layer 406 by thin film deposition program 402 has smooth surface morphology.
Please refer to Figure 13, then can be with reference to as the manufacture method of Fig. 2～5 related embodiment, continuation sequentially forms the element films such as transparency conducting layer 206, photo-electric conversion element 218 and electrode layer 220 on another surperficial B of transparency carrier 202, and then has completed the making of solar battery apparatus 300.In the present embodiment, solar battery apparatus 300, except possessing the lifting photo-electric conversion element 218 that possessed as the solar battery apparatus 200 in the previous embodiment light utilization rate advantage for incident light 250 (seeing Fig. 5), arrives at photo-electric conversion element 218 places by infrared ray filter layer 404 to reduce the light component of the infrared light wavelength in the incident light 250 that enters solar battery apparatus 300 in addition.So can avoid because photo-electric conversion element 218 has absorbed the problem that operating temperature that the light component of the infrared band in incident light 250 causes promotes, thereby the photoelectric conversion efficiency of having guaranteed photo-electric conversion element 218 is not subject to the impact of operating temperature and causes the reduction of the raw electrical efficiency of solar battery apparatus.In addition, the setting by anti-reflecting layer 406 can promote the light component that enters solar battery apparatus 300 and arrive at the visible wavelength in the incident light 250 (seeing Fig. 5) at photo-electric conversion element 218 places.At this, comprise that infrared light filter layer 404 and the NEW TYPE OF COMPOSITE rete structure of anti-reflecting layer 406 contribute to promote stable operation degree and the useful life of solar battery apparatus.
Please refer to Figure 14, the NEW TYPE OF COMPOSITE rete that comprises infrared light filter layer 404 and anti-reflecting layer 406 as shown in figure 13 in being applied to aforementioned solar battery apparatus 300, also be applicable to be integrated in known silicon film solar batteries (silicon thin film solar cell) as shown in Figure 1 device 100 in, improve thus the stable operation degree of solar battery apparatus 100 and the lifting in useful life.At this, the present embodiment is resulting by the enforcement situation of revising as shown in Figure 1, therefore at this, only describes the difference place between two embodiment, and same numeral represents identical member in the accompanying drawings.
In the present embodiment, infrared light filter layer in composite film 404 and anti-reflecting layer 406 can sequentially be formed on another surface with respect to main members such as the transparency conducting layer 104, amorphous silicon membrane (amorphous silicon thin film) photo-electric conversion element 150 that are provided with tin oxide (fluorine doped tinoxide, the FTO) material of fluorine doping and electrode layers 112 on glass substrate 102.And the glass substrate 102 using is not limited with the substrate of glass material, it also can be other transparency carrier of polymeric membrane plate base or flexible base plate.Described in the same, the setting by infrared ray filter layer 404 can reduce the light component that enters 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 because photo-electric conversion element 150 has absorbed the problem that operating temperature that the light component of the infrared band in incident light 180 causes promotes, thereby the photoelectric conversion efficiency of having guaranteed photo-electric conversion element 150 is not subject to the impact of operating temperature and causes the reduction of the raw electrical efficiency of solar battery apparatus.In addition, the setting by anti-reflecting layer 406 can promote the light component that enters solar battery apparatus 100 and arrive at the visible wavelength in the incident light 180 at photo-electric conversion element 150 places.Above-mentionedly comprise that infrared light filter layer 404 and the NEW TYPE OF COMPOSITE rete of anti-reflecting layer 406 contribute to promote 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
First, provide containing 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
4after the LiCl of F and 0.09 mole, obtain a mixed aqueous solution.The air of separately usining passes into a miniature drop atomizer as carrier gas, and after above-mentioned mixed aqueous solution evenly being mixed with air by this miniature drop atomizer, by miniature drop atomizer, be directly directed in through being heated to the test piece of glass material of 400 ℃ to form chemical vapour deposition (CVD) thereon, and then obtained the SnO of the about 800nm of thickness
2: Li:F (Li-FTO) transparency conducting layer, it is comprised of polyhedron naked core as shown in Figure 2 thereby is had rough non-planar form surface, and the path length through measuring this polyhedron naked core is between 200-300nm.At this, the doping that in the transparency conducting layer of resulting Li-FTO material, the doping of Li is about 0.3at% and F is about 0.5at%.Optical field distribution angle through measuring this transparency conducting layer is between 45 °-55 °.By the measurement of atomic force microscope (AFM), polyhedron naked core in the transparency conducting layer of resulting Li-FTO material has approximately 65% naked core distribution density, has shown the surface topography distribution scenario of the transparency conducting layer that comprises polyhedron naked core in Figure 17.
Embodiment 2: the preparation of the transparency conducting layer of tool polyhedron naked core
First, provide containing 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
4after the LiCl of F and 0.12 mole, obtain a mixed aqueous solution.The air of separately usining passes into a miniature drop atomizer as carrier gas, and after above-mentioned mixed aqueous solution evenly being mixed with air by this miniature drop atomizer, by miniature drop atomizer, be directly directed in through being heated to the test piece of glass material of 450 ℃ to form chemical vapour deposition (CVD) thereon, and then obtained the SnO of the about 850nm of thickness
2: Li:F (Li-FTO) (material) transparency conducting layer, it is comprised of polyhedron naked core as shown in Figure 2 thereby is had rough non-planar form surface, and the path length through measuring this polyhedron naked core is between 500-600nm.At this, the doping that in the transparency conducting layer of resulting Li-FTO material, the doping of Li is about 0.5at% and F is about 0.5at%.Optical field distribution angle through measuring this transparency conducting layer is between 65 °-75 °.By the measurement of atomic force microscope (AFM), polyhedron naked core in the transparency conducting layer of resulting Li-FTO material has approximately 75% polyhedron naked core distribution density, has shown the surface topography distribution scenario of the transparency conducting layer that comprises polyhedron naked core in Figure 18.
Comparative example 1: the preparation of the transparency conducting layer of plane configuration
First, provide containing 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
4after F, obtain a mixed aqueous solution.The air of separately usining passes into a miniature drop atomizer as carrier gas, and after above-mentioned mixed aqueous solution evenly being mixed with air by this miniature drop atomizer, by miniature drop atomizer, be directly directed in once being heated to the test piece of glass material of 360 ℃ to form chemical vapour deposition (CVD) thereon, and then obtained the SnO of the about 800nm of thickness
2: Li:F (Li-FTO) transparency conducting layer, it has broadly similar in the plane configuration surface of Fig. 1.At this, in the transparency conducting layer of resulting Li-FTO material, the doping of F is about 0.1at%.By the measurement of atomic force microscope (AFM), polyhedron naked core in the transparency conducting layer of resulting Li-FTO material has the polyhedron naked core distribution density that is less than 30%, thereby transparency conducting layer has the surface topography of almost plane form, in Figure 19, shown the surface topography distribution scenario of the transparency conducting layer of this plane configuration.
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 by 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, maximum at Li element doping amount incident light (wavelength is between 1200～1800nm) reflectivity of (embodiment 2) while being 0.3at% (embodiment 1) with 0.5at% is about 30%, but when the doping of Li during lower than 0.2at% its incident light (wavelength is between 1200～1800nm) reflectivity be about 40-50%.
Absorptivity test:
Fig. 9 shown embodiment 1 and 2 and comparative example 1 in the test result of absorptivity of transparency conducting layer.Measurement by absorption spectrometry (absorption spectroscopy) can be learnt, embodiment 1 and 2 and comparative example 1 in the absorptivity of transparency conducting layer can be along with the variation of the doping of Li element in it significantly change, incident light (wavelength is between 400～800nm) absorptivity in Li element doping amount while being 0.3at% (embodiment 1) with 0.5at% (embodiment 2) is 30%-65%, but when the doping of Li during lower than 0.2at% its incident light (wavelength is between 400～800nm) absorptivity be about 10-50%.
Embodiment 3:
First, provide the SnCl that contains 0.5 mole
25H
2the aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.35 mole of codope
4after the LiCl of F and 0.075 mole to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.The air of separately usining passes into a miniature drop atomizer as carrier gas, and will be containing Sn (OH) by this miniature drop atomizer
4the aqueous solution by miniature drop atomizer, at flow, be under 20L/min, to obtain a size between the gas suspensoid air-flow of 5～8 microns after doing even mixing with air.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of glass material of 400 ℃ to form chemical vapour deposition (CVD) thereon, and then obtains the transparent infrared light filter layer of the main composition of tin oxide of the about 1000nm of thickness.At this, in the transparent infrared light filter layer of the main composition of resulting tin oxide, the doping of Li is about 1.5at% and the doping of F is about 1.0at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Embodiment 4:
First, provide the SnCl that contains 0.5 mole
25H
2the aqueous solution of the tin metal salt of O, and in this aqueous solution the NH of 0.35 mole of codope
4after the LiCl of F and 0.1 mole to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.Separately using air as carrier gas and and pass into a miniature drop atomizer, and by miniature drop atomizer, at flow, be under 20L/min, to obtain a size between the gas suspensoid air-flow of 5～8 microns after the aqueous solution containing Sn (OH) 4 being done to even mixing with air by this miniature drop atomizer.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of the glass material of 400 ℃ and does chemical vapour deposition (CVD), and then obtain the transparent infrared light filter layer of the main composition of tin oxide of the about 1000nm of thickness.At this, in the transparent infrared light filter layer of the main composition of resulting tin oxide, the doping of Li is about 2.0at% and the doping of F is about 2.0at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Embodiment 5:
First, provide the SnCl that contains 0.5 mole
25H
2the aqueous solution of the tin metal salt of O, and in this aqueous solution after the LiCl of the NH4F of 0.35 mole of codope and 0.125 mole to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.The air of separately usining passes into a miniature drop atomizer as carrier gas, and will be containing Sn (OH) by this miniature drop atomizer
4the aqueous solution by miniature drop atomizer, at flow, be under 20L/min, to obtain a size between the gas suspensoid air-flow of 5～8 microns after doing even mixing with air.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of glass material of 400 ℃ to form chemical vapour deposition (CVD) thereon, and then obtains the transparent infrared light filter layer of the main composition of tin oxide of the about 1000nm of thickness.At this, in the transparent infrared light filter layer of the main composition of resulting tin oxide, the doping of Li is about 2.5at% and the doping of F is about 2.6at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Comparative example 2:
First, provide the SnCl that contains 0.5 mole
25H
2the aqueous solution of the tin metal salt of O, and in this aqueous solution after the NH4F of 0.35 mole of codope to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.The air of separately usining passes into a miniature drop atomizer as carrier gas, and will be containing Sn (OH) by this miniature drop atomizer
4the aqueous solution by miniature drop atomizer, at flow, be under 20L/min, to obtain size between the gas suspensoid air-flow of 5～8 microns after doing even mixing with air.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of glass material of 400 ℃ to form chemical vapour deposition (CVD) thereon, and then obtains the transparent red outside line secluding film of the main composition of tin oxide of the about 1000nm of thickness.At this, in the transparent red outside line isolation layer of the main composition of resulting tin oxide, the doping of Li is about 0at% and the doping of F is about 0.5at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.
Light reflectivity test:
Figure 10 has shown the light reflectivity test result of the infrared light filter layer in embodiment 3-5 and comparative example 2.Measurement by reflection spectrometry (reflectance spectroscopy) can be learnt, the incident light reflectivity of the infrared light filter layer in embodiment 3-5 and comparative example 2 can be along with Li, the variation of the doping of the elements such as F and significantly changing, at Li and F element doping amount, be respectively 1.5at% and 1.0at% (embodiment 3), incident light (ripple is longer than 1600nm) reflectivity when 2.0at% and 2.0at% (embodiment 4) and 2.5at% and 2.6at% (embodiment 5) be about respectively 30%, 35% and 40%, but its incident light (ripple is longer than 1600nm) reflectivity is about 5% when the doping of Li and F is respectively 0at% and 0.5at% (comparative example 2).
Light transmittance test:
Figure 11 has shown the light transmittance test result of the infrared light filter layer in embodiment 3-5 and comparative example 2.Measurement by penetrating light spectrometry (transmission spectroscopy) can be learnt, the incident light penetrance of the infrared light filter layer in embodiment 3-5 and comparative example 2 can be along with Li, the variation of the doping of the elements such as F and significantly changing, at Li and F element doping amount, be respectively 1.5at% and 1.0at% (embodiment 3), incident light (ripple is longer than 1400nm) penetrance when 2.0at% and 2.0at% (embodiment 4) and 2.5at% and 2.6at% (embodiment 5) be about respectively 30%, 20% and 10%, but its incident light (ripple is longer than 1600nm) penetrance is about 80% when the doping of Li and F is respectively 0at% and 0.5at% (comparative example 2).
Embodiment 6:
First, provide the SnCl that contains 0.5 mole
25H
2the aqueous solution of the tin metal salt of O, and the NH of 0.25 mole of adulterating in this aqueous solution
4f is to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.The air of separately usining passes into a miniature drop atomizer as carrier gas, and will be containing Sn (OH) by this miniature drop atomizer
4the aqueous solution by miniature drop atomizer, at flow, be under 10L/min, to obtain size between the gas suspensoid air-flow of 10～80 microns after doing even mixing with air.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of glass material of 400 ℃ to form chemical vapour deposition (CVD) thereon, and then obtains the transparent infrared light filter layer of the main composition of tin oxide of the fluorine doping of the about 500nm of thickness.At this, in the transparent infrared light filter layer of the main composition of resulting tin oxide, the doping of fluorine is about 1.0at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.Then, adopt immersion plating method to form the silica membrane that thickness is about 110 nanometers on formed transparent infrared light filter layer, it has the refractive index (n) that is about 1.3.
Embodiment 7:
First, provide the SnCl that contains 0.3 mole
25H
2the aqueous solution of the tin metal salt of O, and the NH4F of 0.5 mole of adulterating in this aqueous solution is to obtain containing Sn (OH)
4the aqueous solution, and by this containing Sn (OH)
4the aqueous solution be placed in a container.The air of separately usining passes into a miniature drop atomizer as carrier gas, and will be containing Sn (OH) by this miniature drop atomizer
4the aqueous solution by miniature drop atomizer, at flow, be under 20L/min, to obtain size between the gas suspensoid air-flow of 5～80 microns after doing even mixing with air.Then, gas suspensoid air-flow is directly directed in through being heated to the test piece of glass material of 380 ℃ to form chemical vapour deposition (CVD) thereon, and then obtains the transparent infrared light filter layer of the main composition of tin oxide of the fluorine doping of the about 130nm of thickness.At this, the doping of the transparent infrared light filter layer F of the main composition of resulting tin oxide is about 1.5at%.The frequency of oscillation of above-mentioned miniature drop atomizer is 1,000KHz.Then, adopt immersion plating method to form the anti-reflecting layer that thickness is about the earth silicon material of 110 nanometers on formed transparent infrared light filter layer, it has the refractive index (n) that is about 1.3.
Comparative example 3-4:
Implement situation with embodiment 6 and 7, after the transparent infrared light filter layer of the main composition of tin oxide only adulterating at the fluorine that forms the about 500nm of thickness or 130nm, form no longer thereon the anti-reflecting layer of earth silicon material.
Light transmittance test:
Figure 15 has shown the light transmittance test result of the sample in embodiment 6 and comparative example 3.Measurement by penetrating light spectrometry (transmission spectroscopy) can be learnt, in as the sample of comparative example 3, by the setting of infrared light filter layer, can show lower than 40% penetrance and penetrate spectra part (for example, in 550nm place) at visible ray at infrared spectrum part (for example, in wavelength 1300nm place) and show the penetrance that is about 80%.And in as the sample of embodiment 6, by the extra setting of anti-reflecting layer, can show almost constant penetrance (also lower than 40%) and penetrate spectra part at visible ray at infrared spectrum part (for example, in wavelength 1300nm place) that to show compared with comparative example 3 be high penetrance (being about 90%).
In addition, Figure 16 has shown the light transmittance test result of the sample in embodiment 7 and comparative example 4.Measurement by penetrating light spectrometry (transmission spectroscopy) can be learnt, in as the sample of comparative example 4, by the setting of infrared light filter layer, can show lower than 40% penetrance and penetrate spectra part (for example, in 550nm place) at visible ray at infrared spectrum part (for example, in wavelength 1700nm place) and show the penetrance that is about 88%.And in as the sample of embodiment 7, by the extra setting of anti-reflecting layer, can show almost constant penetrance (also lower than 40%) and penetrate spectra part at visible ray at infrared spectrum part (for example, in wavelength 1700nm place) that to show compared with comparative example 4 be high penetrance (being about 95%).
Although the present invention discloses as above with preferred embodiment; so it is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, so protection scope of the present invention is when being as the criterion depending on the appended claim person of defining.
Claims (16)
1. a 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 is comprised of 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 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 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 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 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 lithium doping concentration in this lithium and 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 comprise infrared light filter layer and anti-reflecting layer, are sequentially arranged at this transparency carrier upper with respect to a surface of this transparency conducting layer, and 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 through lithium, gallium, fluorine or antimony doping.
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 through fluorine doping, and this tin oxide through fluorine doping is more doped with lithium atom.
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| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4663495A (en) * | 1985-06-04 | 1987-05-05 | Atlantic Richfield Company | Transparent photovoltaic module |
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| JP4959127B2 (en) * | 2004-10-29 | 2012-06-20 | 三菱重工業株式会社 | Photoelectric conversion device and substrate for 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 |
| TWI367530B (en) * | 2007-12-25 | 2012-07-01 | Ind Tech Res Inst | Chlorine, fluorine and lithium co-doped transparent conductive films and methods for fabricating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4663495A (en) * | 1985-06-04 | 1987-05-05 | Atlantic Richfield Company | Transparent photovoltaic module |
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