CN102157693A - Solar battery and manufacturing method thereof - Google Patents
Solar battery and manufacturing method thereof Download PDFInfo
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- CN102157693A CN102157693A CN2011100320970A CN201110032097A CN102157693A CN 102157693 A CN102157693 A CN 102157693A CN 2011100320970 A CN2011100320970 A CN 2011100320970A CN 201110032097 A CN201110032097 A CN 201110032097A CN 102157693 A CN102157693 A CN 102157693A
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Abstract
The invention discloses a solar battery and a manufacturing method thereof. The solar battery comprises a lower electrode component, an upper electrode component, a sealant and an electrolyte, wherein the sealant is used for assembling the lower electrode component and the upper electrode component together to form a closed space; the electrolyte is accommodated in the closed space; the lower electrode component comprises a lower transparent conductive substrate, a nano-oxide semiconductor thin film and a dye, wherein the nano-oxide semiconductor thin film is formed on the lower transparent conductive substrate; the dye is attached to the surfaces of the nano-particles in the nano-oxide semiconductor thin film; the upper electrode component comprises an upper transparent conductive substrate; sunlight is emitted from one side of the upper electrode component, wherein the upper electrode component also comprises an alpha-Si thin-film solar battery formed on the upper transparent conductive substrate; the alpha-Si thin-film solar battery comprises a P-type alpha-Si thin film, an I-type alpha-Si thin film and an N-type alpha-Si thin film stacked in turn; the N-type alpha-Si thin film is arranged opposite to the nano-oxide semiconductor thin film; and the N-type alpha-Si thin film and the nano-oxide semiconductor thin film are contacted with the electrolyte.
Description
Technical field
The present invention relates to solar cell and manufacture method thereof, more specifically, relate to composite solar battery and manufacture method thereof.
Background technology
French scientist Henri Becq μ erel transforms phenomenon in first observed in 1839 to photoelectricity, but but up to the appearance of the semiconductor solar cell of first practicality in 1954, the idea of " conversion of solar energy is become electric energy " just really becomes a reality.In the initial development stage of solar cell, employed material generally is the narrow bandgap semiconductor material that certain absorption is arranged in the visual field, and therefore this solar cell is called semiconductor solar cell again.
Although wide band gap semiconducter itself is caught the non-constant of the ability of sunlight, suitable dyestuff is attached on the semiconductor surface, by means of the strong absorption of dyestuff, can be electric energy also with conversion of solar energy to visible light.This battery is exactly DSSC (DSSC).
1991, the Switzerland scientist
Utilize nanometer technology that the photoelectric conversion efficiency among the DSSC is brought up to 7% first Deng the people.From then on, dye sensitized nano crystal salar battery (promptly
Battery) is born thereupon and is able to fast development.After this, based on
The high-photoelectric transformation efficiency of the novel DSSC of battery has reached 11%.
Fig. 1 shows the schematic sectional view of aforesaid traditional DSSC.This DSSC comprises bottom electrode assembly 10 and top electrode assembly 20.Bottom electrode assembly 10 is included in the lower electrode layer 12 that forms on the lower glass substrate 11, the nanometer oxide semiconductor film 13 that forms on lower electrode layer 12, and the dyestuff (not shown) that adheres on the nano grain surface in nanometer oxide semiconductor film 13.Top electrode assembly 20 is included in the upper electrode layer 22 that forms on the top glass substrate 21.Adopt sealant 31 that bottom electrode assembly 10 and top electrode assembly 20 are fitted together, nanometer oxide semiconductor film 13 and upper electrode layer 22 toward each other, to form confined space.In confined space, hold electrolyte 32 (for example electrolyte solution or solid electrolyte).
Sunlight is the surperficial incident of utmost point assembly 20 1 sides from power on, reaches nanometer oxide semiconductor film 13 in order to make solar energy get at, and top glass substrate 21, upper electrode layer 22 and electrolyte 32 should be printing opacities.For example, upper electrode layer 22 can use FTO (mixing the tin oxide of fluorine) electro-conductive glass.
Yet the photoelectric conversion efficiency of DSSC is difficult to further raising over past ten years.
On the one hand, the absorption spectrum of widely used ruthenium based dye N3, N719 etc. can not mate with solar spectrum in DSSC.For example, the absworption peak of dyestuff N719 (trade name, the product of Switzerland Solaronix company) mainly concentrates on 380nm and 520nm place, and is all very low to the absorptivity of other spectral coverage, thereby can not effectively utilize the sunlight of full spectral coverage.
On the other hand, in the solar cell working process, owing to be subjected to the restriction of electrolyte intermediate ion oxidation/reduction reaction speed institute, the light induced electron of generation and hole are in the process that collector transports separately dyestuff is subjected to optical excitation after, and generation photoelectron/hole-recombination process also generates the ground state dyestuff.And, be transported to nano-TiO at light induced electron through electrolyte as anode
2In the process on the film, a part of light induced electron can be gone back the ortho states electrolyte with the electrolyte generation reduction reaction and the generation of oxidation state, and so-called " dark reaction " process promptly takes place.As a result, cause the loss of light induced electron, reduced the photoelectric conversion efficiency of DSSC." dark reaction " process is to cause the main cause of the loss of light induced electron.
Summary of the invention
The purpose of this invention is to provide a kind of low cost of manufacture and the high solar cell of opto-electronic conversion effect, wherein with the N type district of α-Si solar cell as the electron injection electrode among the DSSC, formed the composite solar battery of the solar cell that comprises two types.
According to an aspect of the present invention, a kind of solar cell is provided, comprise bottom electrode assembly, the top electrode assembly, be used for bottom electrode assembly and top electrode component groups are fitted together and form the sealant of confined space, and be contained in electrolyte in the confined space, wherein bottom electrode assembly comprises transparent conductive substrate down, the nanometer oxide semiconductor film that on following transparent conductive substrate, forms, and the dyestuff that adheres on the nano grain surface in the nanometer oxide semiconductor film, and the top electrode assembly comprises transparent conductive substrate, sunlight utmost point assembly one side incident from power on, wherein said top electrode assembly also is included in the α-Si thin-film solar cells that forms on the transparent conductive substrate, described α-Si thin-film solar cells comprises the P type α-Si film that stacks gradually, I type α-Si film and N type α-Si film, N type α-Si film and nanometer oxide semiconductor film are oppositely arranged, and N type α-Si film contacts with electrolyte with the nanometer oxide semiconductor film.
According to a further aspect in the invention, provide a kind of method of making solar cell, comprise following step mule:
Make the top electrode assembly, wherein form α-Si thin-film solar cells on last transparent conductive substrate, described α-Si thin-film solar cells comprises P type α-Si film, I type α-Si film and the N type α-Si film that stacks gradually;
Make bottom electrode assembly, wherein forming the nanometer oxide semiconductor film on the transparent conductive substrate down, and on the nanometer oxide semiconductor film, adhering to dyestuff; And
Adopt sealant, top electrode assembly and bottom electrode assembly are fitted together, wherein N type α-Si film and nanometer oxide semiconductor film to form confined space, inject electrolyte toward each other in confined space.
In solar cell of the present invention, the absorption spectrum complementation of employed dyestuff in α-Si thin-film solar cells and the DSSC.The battery of this composite construction is realized the absorption spectrum of solar cell and the optimum Match of solar spectrum, thereby improves the absorptivity to sunlight.
α-Si thin-film solar cells is not only as independently battery unit generating, and the photoelectron electric current of the N type district of α-Si thin-film solar cells output is injected in the electrolyte of DSSC, effectively strengthened the oxidation/reduction reaction of electrolyte intermediate ion, suppress so-called dark reaction, can effectively improve the photoelectric conversion efficiency of DSSC.
The result, generating efficiency by DSSC and α-composite solar battery that the Si thin-film solar cells is formed according to the present invention is higher than the generating efficiency sum of DSSC and α-when the Si thin-film solar cells is used separately, thereby has formed composite solar battery efficiently.
And, the manufacturing process compatibility of solar cell of the present invention and existing DSSC, thereby close with any one manufacturing cost of α-Si thin-film solar cells or DSSC, this helps the batch process of solar cell and has reduced manufacturing cost.
Description of drawings
Fig. 1 shows the schematic sectional view of traditional DSSC.
Fig. 2 shows the schematic sectional view according to the solar cell of the first embodiment of the present invention.
Fig. 3 shows the schematic sectional view of solar cell according to a second embodiment of the present invention.
Fig. 4 shows dyestuff N719 and α-Si thin-film solar cells absorption spectrum schematic diagram.
Embodiment
Describe embodiments of the invention below in detail, wherein in institute's drawings attached, adopt identical or similar label to represent identical or similar elements.These embodiment are exemplary, only are used to explain the present invention, and can not be interpreted as limitation of the present invention.
Hereinafter, the structure that embodiment 1 to 2 relates separately to according to solar cell of the present invention, the method that embodiment 3 to 5 relates separately to according to manufacturing solar cell of the present invention.
Embodiment 1
Fig. 2 shows the schematic sectional view according to the solar cell of the first embodiment of the present invention.This solar cell comprises bottom electrode assembly 10 and top electrode assembly 20.
This solar cell is the composite construction of α-Si thin-film solar cells and DSSC, and wherein α-Si thin-film solar cells is arranged on the upper electrode layer 22 of DSSC, comprises P type α-Si film 23, I type α-Si film 24 and N type α-Si film 25.
α-Si thin-film solar cells is based on the photovoltaic effect of PN junction.α-Si is a kind of aboundresources and environmentally safe material, and is very high to the absorptivity of sunlight.The manufacture method of α-Si thin-film solar cells is known, and wherein α-Si thin-film material can directly be deposited on the inexpensive substrate at (below 300 ℃) under the lower temperature, has reduced manufacturing cost significantly.
The inventor notices the complementary characteristic of the absorption spectrum of the absorption spectrum of α-Si thin-film solar cells and ruthenium based dye (for example dyestuff N719).Fig. 4 shows dyestuff N719 and α-Si thin-film solar cells absorption spectrum schematic diagram, and wherein, curve a represents the absorption spectrum of dyestuff N719, and curve b represents the absorption spectrum of α-Si solar cell.Dyestuff N719 shows absworption peak about 380nm and 520nm, and α-Si solar cell shows absworption peak about 600nm.
As can be seen from Figure 4, utilize the composite solar battery of the α of comprising of the present invention-Si thin-film solar cells and DSSC, can absorb sunlight expeditiously in wide wave-length coverage, realize the absorption spectrum of solar cell and the optimum Match of solar spectrum, thereby improve absorptivity sunlight.
And, the N type district of α-Si thin-film solar cells injects photoelectron as electron injection electrode in the electrolyte 32 of DDSC, effectively strengthened the oxidation/reduction reaction of electrolyte intermediate ion, suppress the dark reaction process, can further improve photoelectric conversion efficiency.
Embodiment 2
Fig. 3 shows the schematic sectional view of solar cell according to a second embodiment of the present invention.The structure of the solar cell of the solar cell of second embodiment and first embodiment is basic identical, difference only is to use down transparent conductive substrate 11 ' to replace comprising the lamination of lower glass substrate 11 and lower electrode layer 12, and uses and go up the lamination that transparent conductive substrate 21 ' replaces comprising top glass substrate 21 and upper electrode layer 22.
With respect to first embodiment, the transparent conductive substrate in the solar cell of second embodiment plays the effect of electrode layer, thereby can omit the depositing step that is used to form lower electrode layer 12 and upper electrode layer 22, further simplified manufacturing technique.
Utilize the composite solar battery of the α of comprising of the present invention-Si thin-film solar cells and DSSC, can improve the absorptivity of sunlight and suppress the dark reaction process, thus the photoelectric conversion efficiency of raising solar cell.
Embodiment 3
Method according to this embodiment is used to make the composite solar battery of being made up of α-Si thin-film solar cells and DSSC.
At first, make top electrode assembly 20 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the last transparent conductive substrate 21 ' in the bottom electrode assembly 20.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Utilize plasma-reinforced chemical vapor deposition (PECVD) manufactured amorphous silicon membrane, in the α-Si thin-film solar cells of transparent conductive substrate 21 ' formation P-I-N structure, wherein, three key reaction formulas among the PECVD are as follows:
SiH
4=Si+2H
2(deposit Si) 2PH
3=2P+3H
2(mixing P) B
2H
6=2B+3H
2(mixing B).
At first go up deposit P type α-Si film 23 at transparent conductive substrate 21 '.Reative cell is evacuated the silane (SiH that proportioning is good
4), borine (B
2H
6), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2) the feeding reative cell, reconcile the flow of all gases, the air pressure that makes reative cell at 6.665Pa between the 666.5Pa, the frequency of using is that 50Hz is to 13.56MHz, between positive and negative electrode, add-1 then～-the 5kV back bias voltage, go out electronics by cathode emission, and in electric field, obtain indoor gas molecule or the atom of crash response behind the energy, make it to decompose, excite or ionization, form plasma.The final silicon atom that decomposes deposits on substrate, forms amorphous silicon membrane.Wherein, silane concentration is more than 10%, and flow is 50～200mL/min, and underlayer temperature is 200～300 ℃, and power is at 300～500w/m
2, the relatively more suitable amorphous silicon membrane of making.The thickness of P type α-Si film 23 is about 0.2um.
Deposit I type α-Si film 24 on P type α-Si film 23 subsequently, the gas that feed this moment is silane (SiH
4), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of I type α-Si film 24 is about 0.7um.
Deposit N type α-Si film 25 on I type α-Si film 24 at last, the gas that feed this moment is silane (SiH
4), phosphine (PH
3), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of N type α-Si film 25 is about 0.2um.
Preferably, step original position in same reative cell of above-mentioned formation P type α-Si film, I type α-Si film and N type α-Si film is carried out
Further, make top electrode assembly 10 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the following transparent conductive substrate 11 ' in the bottom electrode assembly 10.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Then, make nano-TiO
2Slurry.At first get the commercial TiO that German Degussa company produces
2P25 particle 6g dissolve in 1ml acetate and mix, put into mortar and grind and add the 1ml deionized water after 1～3 minute and continue to grind 1 minute, so repeat 3～5 times.Add 1ml ethanol (ethanol of being mentioned among the embodiment is all absolute ethyl alcohol) after finishing and ground 1 minute, so repeat 10～20 times and add 2.5ml ethanol grinding 1 minute afterwards again, so repeat 3～5 times.After all above-mentioned grinding work all finish, with the TiO that forms
2Transfer in the beaker, stirred 2 minutes behind the ethanol of adding 100ml.Continue to stir 2 minutes after in beaker, adding 10～18g sesame oil brain.Next step adds ethyl cellulose, is dissolved in the ethanolic solution according to the proportioning of 3g (ethyl cellulose): 30g (the absolute ethyl alcohol total amount that adds in the present embodiment), stirs 6 minutes.After all stir end-of-jobs, after the ethanol evaporation in the beaker gone out, TiO
2Slurry is just made and has been finished.
Next, adopt screen process press, with the TiO for preparing
2Slurry is printed on the transparent conductive substrate 21 '.After printing, on electric hot plate, remove moisture with 50～80 ℃ of baking 5～8min, will descend transparent conductive substrate 11 ' to place Muffle furnace to toast 1～3 hour down for 300～450 ℃ again.Thereby, form nanometer oxide semiconductor film 13 at following transparent conductive substrate 11 '.
In this embodiment, nanometer oxide semiconductor film 13 is about the nano-TiO of 10 μ m for thickness
2Film, TiO
2The mean radius of particle is about 25nm.
Then, will descend transparent conductive substrate 11 ' to immerse in the dyestuff 16 hours with at TiO
2The surface attachment dyestuff of particle.
Further, according to following steps top electrode assembly 10 and bottom electrode assembly 20 compositions are formed solar cell together.
Adopt sealant 31 that bottom electrode assembly 10 and top electrode assembly 20 are fitted together, N type α-Si film 25 and nanometer oxide semiconductor film 13 toward each other, to form confined space.In confined space, inject electrolyte 32 (for example electrolyte solution or solid electrolyte).
The solar cell that assembling is finished as shown in Figure 3.N type α in the top electrode assembly 20-Si film 25 contact electrolyte 32 as the electron injection electrode of DSSC, injects the photoelectron electric current in electrolyte 32 when being subjected to solar light irradiation.
Method according to this embodiment is used to make the composite solar battery of being made up of α-Si thin-film solar cells and DSSC.
At first, make top electrode assembly 20 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the last transparent conductive substrate 21 ' in the bottom electrode assembly 20.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Utilize plasma-reinforced chemical vapor deposition (PECVD) manufactured amorphous silicon membrane, in the α-Si thin-film solar cells of transparent conductive substrate 21 ' formation P-I-N structure, wherein, three key reaction formulas among the PECVD are as follows:
SiH
4=Si+2H
2(deposit Si) 2PH
3=2P+3H
2(mixing P) B
2H
6=2B+3H
2(mixing B).
At first go up deposit P type α-Si film 23 at transparent conductive substrate 21 '.Reative cell is evacuated the silane (SiH that proportioning is good
4), borine (B
2H
6), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2) the feeding reative cell, reconcile the flow of all gases, the air pressure that makes reative cell at 6.665Pa between the 666.5Pa, the frequency of using is that 50Hz is to 13.56MHz, between positive and negative electrode, add-1 then～-the 5kV back bias voltage, go out electronics by cathode emission, and in electric field, obtain indoor gas molecule or the atom of crash response behind the energy, make it to decompose, excite or ionization, form plasma.The final silicon atom that decomposes deposits on substrate, forms amorphous silicon membrane.Wherein, silane concentration is more than 10%, and flow is 50～200mL/min, and underlayer temperature is 200～300 ℃, and power is at 300～500w/m
2, the relatively more suitable amorphous silicon membrane of making.The thickness of P type α-Si film 23 is about 0.2um.
Deposit I type α-Si film 24 on P type α-Si film 23 subsequently, the gas that feed this moment is silane (SiH
4), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of I type α-Si film 24 is about 0.7um.
Deposit N type α-Si film 25 on I type α-Si film 24 at last, the gas that feed this moment is silane (SiH
4), phosphine (PH
3), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of N type α-Si film 25 is about 0.2um.
Preferably, step original position in same reative cell of above-mentioned formation P type α-Si film, I type α-Si film and N type α-Si film is carried out
Further, make top electrode assembly 10 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the following transparent conductive substrate 11 ' in the bottom electrode assembly 10.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Then, make nano-TiO
2Slurry.At first get the commercial TiO that German Degussa company produces
2P25 particle 6g dissolve in 1ml acetate and mix, put into mortar and grind and add the 1ml deionized water after 3～8 minutes and continue to grind 1 minute, so repeat 5～8 times.Add 1ml ethanol (ethanol of being mentioned among the embodiment is all absolute ethyl alcohol) after finishing and ground 1 minute, so repeat 20～30 times and add 2.5ml ethanol grinding 1 minute afterwards again, so repeat 5～10 times.After all above-mentioned grinding work all finish, with the TiO that forms
2Transfer in the beaker, stirred 2 minutes behind the ethanol of adding 100ml.Continue to stir 2 minutes after in beaker, adding 18～30g sesame oil brain.Next step adds ethyl cellulose, is dissolved in the ethanolic solution according to the proportioning of 3g (ethyl cellulose): 30g (the absolute ethyl alcohol total amount that adds in the present embodiment), stirs 6 minutes.After all stir end-of-jobs, after the ethanol evaporation in the beaker gone out, TiO
2Slurry is just made and has been finished.
Next, adopt screen process press, with the TiO for preparing
2Slurry is printed on the transparent conductive substrate 21 '.After printing, on electric hot plate, remove moisture with 80～120 ℃ of baking 8～12min, will descend transparent conductive substrate 11 ' to place Muffle furnace to toast 1～3 hour down for 450～600 ℃ again.Thereby, form nanometer oxide semiconductor film 13 at following transparent conductive substrate 11 '.
In this embodiment, nanometer oxide semiconductor film 13 is about the nano-TiO of 10 μ m for thickness
2Film, TiO
2The mean radius of particle is about 25nm.
Then, will descend transparent conductive substrate 11 ' to immerse in the dyestuff 16 hours with at TiO
2The surface attachment dyestuff of particle.
Further, according to following steps top electrode assembly 10 and bottom electrode assembly 20 compositions are formed solar cell together.
Adopt sealant 31 that bottom electrode assembly 10 and top electrode assembly 20 are fitted together, N type α-Si film 25 and nanometer oxide semiconductor film 13 toward each other, to form confined space.In confined space, inject electrolyte 32 (for example electrolyte solution or solid electrolyte).
The solar cell that assembling is finished as shown in Figure 3.N type α in the top electrode assembly 20-Si film 25 contact electrolyte 32 as the electron injection electrode of DSSC, injects the photoelectron electric current in electrolyte 32 when being subjected to solar light irradiation.
Method according to this embodiment is used to make the composite solar battery of being made up of α-Si thin-film solar cells and DSSC.
At first, make top electrode assembly 20 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the last transparent conductive substrate 21 ' in the bottom electrode assembly 20.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Utilize plasma-reinforced chemical vapor deposition (PECVD) manufactured amorphous silicon membrane, in the α-Si thin-film solar cells of transparent conductive substrate 21 ' formation P-I-N structure, wherein, three key reaction formulas among the PECVD are as follows:
SiH
4=Si+2H
2(deposit Si) 2PH
3=2P+3H
2(mixing P) B
2H
6=2B+3H
2(mixing B).
At first go up deposit P type α-Si film 23 at transparent conductive substrate 21 '.Reative cell is evacuated the silane (SiH that proportioning is good
4), borine (B
2H
6), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2) the feeding reative cell, reconcile the flow of all gases, the air pressure that makes reative cell at 6.665Pa between the 666.5Pa, the frequency of using is that 50Hz is to 13.56MHz, between positive and negative electrode, add-1 then～-the 5kV back bias voltage, go out electronics by cathode emission, and in electric field, obtain indoor gas molecule or the atom of crash response behind the energy, make it to decompose, excite or ionization, form plasma.The final silicon atom that decomposes deposits on substrate, forms amorphous silicon membrane.Wherein, silane concentration is more than 10%, and flow is 50～200mL/min, and underlayer temperature is 200～300 ℃, and power is at 300～500w/m
2, the relatively more suitable amorphous silicon membrane of making.The thickness of P type α-Si film 23 is about 0.2um.
Deposit I type α-Si film 24 on P type α-Si film 23 subsequently, the gas that feed this moment is silane (SiH
4), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of I type α-Si film 24 is about 0.7um.
Deposit N type α-Si film 25 on I type α-Si film 24 at last, the gas that feed this moment is silane (SiH
4), phosphine (PH
3), methane (CH
4), high-purity argon (Ar), High Purity Hydrogen (H
2), other conditions are with deposit P type α-Si film 23 is identical.The thickness of N type α-Si film 25 is about 0.2um.
Preferably, step original position in same reative cell of above-mentioned formation P type α-Si film, I type α-Si film and N type α-Si film is carried out
Further, make top electrode assembly 10 according to following steps.
FTO (mixing the tin oxide of fluorine (the F)) electro-conductive glass that uses Japanese Nippon Sheet Glass company is as the following transparent conductive substrate 11 ' in the bottom electrode assembly 10.The FTO electro-conductive glass cleans the back oven dry through ultrasonic water bath.
Then, make nano-TiO
2Slurry.At first get the commercial TiO that German Degussa company produces
2P25 particle 6g dissolve in 1ml acetate and mix, put into mortar and grind 5 minutes (preferably) and add the 1ml deionized water afterwards and continue grinding 1 minute, so repeat 5 times (preferably).Add 1ml ethanol (ethanol of being mentioned among the embodiment is all absolute ethyl alcohol) after finishing and ground 1 minute, so repeat 15 times (preferably) and add 2.5ml ethanol grinding 1 minute afterwards again, so repeat 6 times (preferably).After all above-mentioned grinding work all finish, with the TiO that forms
2Transfer in the beaker, stirred 2 minutes behind the ethanol of adding 100ml.Continue to stir 2 minutes after in beaker, adding 20g (preferably) sesame oil brain.Next step adds ethyl cellulose, is dissolved in the ethanolic solution according to the proportioning of 3g (ethyl cellulose): 30g (the absolute ethyl alcohol total amount that adds in the present embodiment), stirs 6 minutes.After all stir end-of-jobs, after the ethanol evaporation in the beaker gone out, TiO
2Slurry is just made and has been finished.
Next, adopt screen process press, with the TiO for preparing
2Slurry is printed on the transparent conductive substrate 21 '.After printing, on electric hot plate, remove moisture with 80 ℃ (preferably) baking 10min (preferably), will descend transparent conductive substrate 11 ' to place Muffle furnace 500 ℃ (preferably) to toast 2 hours (preferably) down again.Thereby, form nanometer oxide semiconductor film 13 at following transparent conductive substrate 11 '.
In this embodiment, nanometer oxide semiconductor film 13 is about the nano-TiO of 10 μ m for thickness
2Film, TiO
2The mean radius of particle is about 25nm.
Then, will descend transparent conductive substrate 11 ' to immerse in the dyestuff 16 hours with at TiO
2The surface attachment dyestuff of particle.
Further, according to following steps top electrode assembly 10 and bottom electrode assembly 20 compositions are formed solar cell together.
Adopt sealant 31 that bottom electrode assembly 10 and top electrode assembly 20 are fitted together, N type α-Si film 25 and nanometer oxide semiconductor film 13 toward each other, to form confined space.In confined space, inject electrolyte 32 (for example electrolyte solution or solid electrolyte).
The solar cell that assembling is finished as shown in Figure 3.N type α in the top electrode assembly 20-Si film 25 contact electrolyte 32 as the electron injection electrode of DSSC, injects the photoelectron electric current in electrolyte 32 when being subjected to solar light irradiation.
Each embodiment of the method for having used transparent conductive substrate to form solar cell shown in Figure 3 has been described in above embodiment 3-5, yet, it will be appreciated by those skilled in the art that by use glass substrate and on electro-conductive glass the deposition of electrode layer replace transparent conductive substrate, can form solar cell shown in Figure 2.
Abovely the present invention has been given explanation with reference to embodiments of the invention.But these embodiment only are for illustrative purposes, and are not in order to limit the scope of the invention.Scope of the present invention is limited by claims and equivalent thereof.Do not depart from the scope of the present invention, those skilled in the art can make a variety of substitutions and modifications, and these substitutions and modifications all should fall within the scope of the present invention.
Claims (16)
1. solar cell, comprise bottom electrode assembly, the top electrode assembly, be used for bottom electrode assembly and top electrode component groups are fitted together and form the sealant of confined space, and be contained in electrolyte in the confined space, wherein bottom electrode assembly comprises transparent conductive substrate down, the nanometer oxide semiconductor film that on following transparent conductive substrate, forms, and the dyestuff that adheres on the nano grain surface in the nanometer oxide semiconductor film, and the top electrode assembly comprises transparent conductive substrate, sunlight utmost point assembly one side incident from power on
Wherein said top electrode assembly also is included in the α-Si thin-film solar cells that forms on the transparent conductive substrate, described α-Si thin-film solar cells comprises P type α-Si film, I type α-Si film and the N type α-Si film that stacks gradually, N type α-Si film and nanometer oxide semiconductor film are oppositely arranged, and N type α-Si film contacts with electrolyte with the nanometer oxide semiconductor film.
2. solar cell according to claim 1, the absorption spectrum of wherein said α-Si thin-film solar cells and the absorption spectrum complementation of dyestuff.
3. solar cell according to claim 2, wherein said dyestuff are dyestuff N719.
4. solar cell according to claim 1, wherein said transparent conductive substrate down and described at least one that goes up in the transparent conductive substrate are the FTO electro-conductive glass.
5. solar cell according to claim 1, wherein said transparent conductive substrate down and described at least one that goes up in the transparent conductive substrate comprise glass substrate and the electrode layer that forms on glass substrate.
6. method of making solar cell may further comprise the steps:
Make the top electrode assembly, wherein form α-Si thin-film solar cells on last transparent conductive substrate, described α-Si thin-film solar cells comprises P type α-Si film, I type α-Si film and the N type α-Si film that stacks gradually;
Make bottom electrode assembly, wherein forming the nanometer oxide semiconductor film on the transparent conductive substrate down, and on the nanometer oxide semiconductor film, adhering to dyestuff; And
Adopt sealant, top electrode assembly and bottom electrode assembly are fitted together, wherein N type α-Si film and nanometer oxide semiconductor film to form confined space, inject electrolyte toward each other in confined space.
7. method according to claim 6, the absorption spectrum of wherein said α-Si thin-film solar cells and the absorption spectrum complementation of dyestuff.
8. method according to claim 7, wherein said dyestuff are dyestuff N719.
9. method according to claim 6, wherein said transparent conductive substrate down and described at least one that goes up in the transparent conductive substrate are the FTO electro-conductive glass.
10. method according to claim 6, wherein said transparent conductive substrate down and described at least one that goes up in the transparent conductive substrate comprise glass substrate and the electrode layer that forms on glass substrate.
11. method according to claim 6 wherein in the step of making the top electrode assembly, adopts plasma-reinforced chemical vapor deposition to form P type α-Si film, I type α-Si film and N type α-Si film.
12. method according to claim 11, the step original position in same reative cell that wherein forms P type α-Si film, I type α-Si film and N type α-Si film is carried out.
13. method according to claim 12 wherein in the step that forms P type α-Si film, adopts borine that P type dopant is provided.
14. method according to claim 12 wherein in the step that forms N type α-Si film, adopts phosphine that N type dopant is provided.
15. method according to claim 6 wherein in the step of making bottom electrode assembly, adopts silk screen printing forming the nanometer oxide semiconductor film on the transparent conductive substrate down.
16. method according to claim 15 wherein in the step of silk screen printing, is used nano-TiO
2Slurry.
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