CN102403130A - Method for manufacturing array nano tube type solar cell thin film - Google Patents
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- CN102403130A CN102403130A CN2010102770370A CN201010277037A CN102403130A CN 102403130 A CN102403130 A CN 102403130A CN 2010102770370 A CN2010102770370 A CN 2010102770370A CN 201010277037 A CN201010277037 A CN 201010277037A CN 102403130 A CN102403130 A CN 102403130A
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Abstract
The invention relates to a method for manufacturing an array nano tube type solar cell thin film, which comprises the following steps of: firstly, preparing a same directivity type silicon substrate and sputtering out a titanized metal layer on the surface of the same directivity type silicon substrate to form a titanized silicon substrate; then, sequentially carrying out vacuum heat treatment operation and annealing heat treatment operation on the titanized silicon substrate, so that the titanized metal layer is transformed into an interjacent phase titanium metal layer; carrying out anode treatment operation on the interjacent phase titanium metal layer, so that the interjacent phase titanium metal layer is transformed into the array nano tube type solar cell thin film and the surface of the array nano tube type solar cell thin film is provided with a plurality of titanium dioxide (TiO2) nano tubes which are arranged in a dense array; and finally, applying a reverse voltage so that the array nano tube type solar cell thin film is separated from the same directivity type silicon substrate. Due to the adoption of the method, a large contact area can be formed between titanium dioxide on the surface of the array nano tube type solar cell thin film and photosensitive dye so as to improve the photoelectric conversion efficiency of a solar cell, thereby more efficiently obtaining electric energy capable of being utilized by people.
Description
Technical field
The present invention is meant a kind of manufacture method of utilizing the nano-tube shaped solar battery thin film of array of silicon garden sheet manufacturing especially about a kind of manufacture method of solar battery thin film.
Background technology
Look about the residing living environment of present masses, because industrial expansion makes the energy in the whole world be consumed just rapidly.By the survey report that many scholar's expert investigations come out, the mankind come to realise gradually and oneself are at present the crucial age of energy critical shortage, and global various countries competitively develop the pollution-free and callable renewable energy resources invariably.According to the estimation of american energy office, to start at from 2003, the irreproducibility energy of oil, natural gas and coal etc. will be exhausted in 41 years, 67 years and 192 years respectively.Under these circumstances, the exploitation of renewable energy resources technology such as solar energy, wind-force, underground heat, biological energy source will certainly more and more come into one's own.
In the middle of numerous renewable energy resources technology, because that solar energy has power generation process is pollution-free and need not the characteristic of standing charges, so generally receive the favor of countries in the world at present, thereby become to making solar cell market flourish fast in recent years.Putting before this, relevant solar energy development subject under discussion day by day comes into one's own, thereby orders about many countries and take up to carry out the new forms of energy policy one after another, and implements the subsidy incentive method, in the hope of develop actively with promote solar cell.
According to expert's statistical result showed, the energy of annual radiation to the earth of the sun is about 5.4 * 10
24Joule, and the annual required energy in the whole world is about 1.1 * 10
20Joule; Therefore, if human can utilize fully from 50,000 of the energy of solar radiation to the earth/, the then human present many energy problems that face just can be readily solved at once.In view of this, be necessary that the develop actively solar cell is in the hope of relieving energy problem in fact.
Look about in the manufacturing technology of existing solar cell, because the processing of wet type solar cell is easy and its conversion efficiency can reach 10%, obvious its very likely can become the main flow of following solar battery technology.Along with the development of nanometer technology, the grasp of human physical structure and chemical characteristic to various materials can extend to the microcosmos of nanometer gradually.In recent years, because partly the expert lets the manufacturing technology of solar cell and usefulness produce revolutionary important breakthrough actively with the field of solar cells that is introduced into of nanometer technology especially, make solar product can meet the user demand of people's livelihood articles for use gradually.
Review to calendar year 2001, the solar power generation amount only accounts for 0.1% of global power consumption, and solar energy industry continues to grow up with annual 35～40% speed.Yet by 2005, global photovoltaic (Photovoltaic) total installation of generating capacity reached 2200 megavolts, about 3,000,000,000 thousand watts-hour of annual energy output.Estimated for the end of the year 2010, the scale in global solar photoelectric market will be above 50,000,000,000 dollars.
Further discuss, the kind of present solar cell is broadly divided into: (1) list/polysilicon solar cell (Mono/Polycrystalline Solar Cell); (2) amorphous silicon/thin-film solar cells (Amorphous/Thin Film Solar Cell); (3) inorganic semiconductor (Inorganic Solar Cell); (4) organic polymer solar cell (Organic Solar Cell); And (5) DSSC (Dye-Sensitized Solar Cell; DSSC).Wherein, since Switzerland scientist Gratzel proposed its DSSC construction package and operation principle in 1991, many experts proposed multiple titanium dioxide (TiO2) film, particle and nanotube (NT, solar energy manufacturing technology nanotubes) in succession.
(patent name is " large-area dye-sensitized solar battery and hot melt thereof are penetrated the spraying manufacturing approach " with TaiWan, China patent the 097132538th (application) number; Hereinafter to be referred as " ' No. 538 patent cases ") be example; Wherein disclosed a kind of large-area dye-sensitized solar battery; It comprises: a base material has titanium dioxide (TiO on it
2) nanotube, with anode as battery; Light-sensitive coloring agent is adsorbed in the surface of titania nanotube; Transparent conductive cathode is provided with respect to anode, and at surface attachment platinum (Pt) the nano-catalyst layer of transparent conductive cathode; And electrolyte; Be encapsulated between anode and the transparent conductive cathode; Wherein titania nanotube is penetrated spraying process via hot melt titanium (Ti) is sprayed on the surface of base material, to produce the titanium sprayed coating, then the titanium sprayed coating is carried out anode treatment and heat treatment and forms.
Processing about the positive plate of solar cell comprises following steps: penetrate spraying process with hot melt titanium is sprayed on the surface of base material, and produce the titanium sprayed coating; Then the titanium sprayed coating is carried out anode treatment and heat treatment to form titania nanotube, so as to the positive plate as solar cell.Yet those skilled in the art all can understand such as, and the contact area and the photoelectric conversion efficiency of the titanium dioxide of light-sensitive coloring agent and positive plate (comprising titania nanotube and the titanium dioxide that does not form titania nanotube) are closely bound up.Because in the technology that No. 538 the patent case is disclosed of ', base material does not possess arrangement directive property known, and when the spraying titanium, be mixed with impurity easily and make cause such as titanium purity reduction; Cause on the positive plate of produced solar cell, the density that titania nanotube distributes is comparatively sparse, and its length is also shorter.
In order to improve photoelectric conversion efficiency; This case inventor thinks the manufacturing technology that is necessary to develop a kind of new nano-tube shaped solar battery thin film of array; Length and distribution density so as to the titania nanotube that increases the nano-tube shaped solar battery thin film of array; Phase can effectively increase the contact area of light-sensitive coloring agent and titanium dioxide when utilizing the nano-tube shaped solar battery thin film of this array to make positive plate.
Summary of the invention
Technical problem and purpose that institute of the present invention desire solves:
Take a broad view of the above, in known technology,,, and when the spraying titanium, be mixed with impurity easily and make cause such as titanium purity reduction because base material does not possess arrangement directive property particularly known in the technology that No. 538 the patent case is disclosed of '; Cause on the positive plate of produced solar cell, the density that titania nanotube distributes is comparatively sparse, and its length is also shorter, more can therefore produce the not enough problem of contact area of light-sensitive coloring agent and titanium dioxide.
Therefore; The manufacture method of the nano-tube shaped solar battery thin film of a kind of array is provided during main purpose of the present invention; Wherein be with one have single arrangement directive property same sensing type silicon substrate as base material, and utilize the mode of sputter to make to be coated on titanizing metal level to have higher Ti content with the surface of sensing type silicon substrate.By this, can make the surface of the produced nano-tube shaped solar battery thin film of array have a plurality of titania nanotubes of arranging with a closely spaced array, and make titania nanotube have long length.
The present invention provides the manufacture method of the nano-tube shaped solar battery thin film of a kind of array for the technological means that problem adopted that solves known technology; This manufacture method is to prepare together sensing type silicon substrate earlier, and goes out a titanizing metal level to form a titanizing silicon substrate at the surperficial sputter with sensing type silicon substrate.Then; In a vacuum heat environment, the titanizing silicon substrate is carried out a vacuum heat operation; So as to elimination titanizing metal level and with the residual stress between sensing type silicon substrate; And continue and in an annealing heat treatment environment, the titanizing silicon substrate is carried out an annealing heat treatment operation, make the titanizing metal level be transformed into one and be situated between at the phase titanium coating.Then, carry out an anode treatment operation at the phase titanium coating, be transformed into the nano-tube shaped solar battery thin film of array at the phase titanium coating, make its surface have a plurality of titanium dioxide (TiO that arrange with a closely spaced array so as to making Jie to being situated between
2) nanotube.At last, apply a revers voltage, make the nano-tube shaped solar battery thin film of array from breaking away from sensing type silicon substrate.
Preferably, Jie mainly can be made up of the sharp ore deposit of titanium dioxide type (anatase phase) crystalline texture at the phase titanium coating; Above-mentioned same sensing type silicon substrate can be together sensing type silicon garden sheet; Go out an operation electricity slurry vapour deposition (Plasma Vapor Deposition capable of using of a titanizing metal level at surperficial sputter with sensing type silicon substrate; PVD) equipment carries out; The pressure of vacuum heat environment can be 0.01torr, and the temperature of vacuum heat environment can be 920 ℃; And the temperature of annealing heat treatment environment can be 850 ℃, and the annealing heat treatment operation can be kept 1 hour.
To being situated between before the phase titanium coating carries out an anode treatment operation, an electrobrightening capable of using (Electrolytic Polishing) operation is cleaned and is polished the titanizing metal level.When carrying out above-mentioned anode treatment operation, be that Jie is immersed in the electrolyte at the phase titanium coating, and apply an operating voltage.Preferably; When carrying out above-mentioned anode treatment operation; Can utilize an electrochemistry direct current polarization curved scanning (Electrochemistry DC Polarization Curve Scanning) operation earlier; Assess out an optimization operational voltage value of above-mentioned operating voltage and an optimization electrolyte pH-value of above-mentioned electrolyte, apply above-mentioned operating voltage according to the optimization operational voltage value, and according to optimization electrolyte pH-value modulation electrolyte.
In addition; In the preferable enforcement of the present invention; When the area of titanizing silicon substrate is 2cm * 2cm; Can above-mentioned optimization operational voltage value be set at 10V to 20V, and can be, make hydrofluoric acid (the Hydrofluoric Acid that comprises 1.2vol.% (concentration expressed in percentage by volume) in the modulation prescription of electrolyte according to optimization electrolyte pH-value; HF) and the sulfuric acid of 10vol.% (Sulfuric Acid; H
2SO
4) wait raw material.
Beneficial functional of the present invention is; Compared to utilizing the produced dye sensitized solar battery anode plate of known technology, though its surface also has titania nanotube, because base material does not possess arrangement directive property; And be mixed with impurity easily during titanium and make cause such as titanium purity reduction in spraying; Cause on the positive plate of produced solar cell, the density that titania nanotube distributes is comparatively sparse, and its length is also shorter.Yet; Can know via experiment proof or qualitative analysis; In the present invention and since be with same sensing type silicon substrate with single arrangement directive property as base material, and utilize the mode of sputter to make to be coated on titanizing metal level to have higher causes such as Ti content with the surface of sensing type silicon substrate; Therefore, the surface of the produced nano-tube shaped solar battery thin film of array has a plurality of titania nanotubes of arranging with a closely spaced array, and makes titania nanotube have long length.
Whereby, can make the titanium dioxide (comprising titania nanotube and the titanium dioxide that does not form titania nanotube) on the nano-tube shaped solar battery thin film of array surface have bigger surface area.When utilizing the nano-tube shaped solar battery thin film of the produced array of the present invention to come the manufacturing solar cells positive plate; Can make between surperficial titanium dioxide of the nano-tube shaped solar battery thin film of array and the light-sensitive coloring agent and have bigger contact area; So as to promoting the photoelectric conversion efficiency of solar cell, and then obtain to supply human use's electric energy more efficiently.
Describe the present invention below in conjunction with accompanying drawing and specific embodiment, but not as to qualification of the present invention.
Description of drawings
Fig. 1 shows together sensing type silicon substrate;
Fig. 2 demonstration utilizes a sputter operation, is plating the titanizing metal level with sensing type silicon substrate to form the titanizing silicon substrate;
Fig. 3 shows that the titanizing metal level is transformed into Jie at the phase titanium coating through behind the annealing heat treatment operation;
Fig. 4 is presented at being situated between after the phase titanium coating carries out the anode treatment operation, makes Jie be transformed into the nano-tube shaped solar battery thin film of array at the phase titanium coating;
Fig. 5 A to Fig. 5 G is presented under the different operating voltages, and the nano-tube shaped solar battery thin film of formed array is institute's images displayed under electron microscope;
After Fig. 6 was presented at and applies a revers voltage, the nano-tube shaped solar battery thin film of array was from breaking away from sensing type silicon substrate;
One of them titanium dioxide unit structure of Fig. 7 displayed map 6; And
Fig. 8 shows the simple making method flow chart of the nano-tube shaped solar battery thin film of array that preferred embodiment of the present invention discloses.
Wherein, Reference numeral
100 titanizing silicon substrates
1 with sensing type silicon substrate
2 titanizing metal levels
2a is situated between at the phase titanium coating
The nano-tube shaped solar battery thin film of 2b array
21b titanium dioxide base film layer
The 22b titania nanotube
The 221b bottom surface
The 222b end face
The 223b internal face
The 224b outside wall surface
The Ri bore
The Ro external diameter of pipe
The L pipe range
A0 unit on average takies surface area
The A1 base area
The A2 top surface area
A3 internal face area
A4 outside wall surface area
Embodiment
Below in conjunction with accompanying drawing and specific embodiment technical scheme of the present invention being carried out detailed description, further understanding the object of the invention, scheme and effect, but is not the restriction as accompanying claims protection range of the present invention.
Because the manufacture method of the nano-tube shaped solar battery thin film of array provided by the present invention can be widely used in the positive plate of making various solar cells, particularly is applied to make DSSC (Dye-Sensitized Solar Cell; DSSC) positive plate, its combination execution mode is too numerous to enumerate especially, so give unnecessary details no longer one by one at this, just lists one of them preferred embodiment of act and specifies, and quote relevant experimental result and verify aforesaid effect.
See also Fig. 1 to Fig. 3, wherein, Fig. 1 shows together sensing type silicon substrate; Fig. 2 demonstration utilizes a sputter operation, is plating the titanizing metal level with sensing type silicon substrate to form the titanizing silicon substrate; And Fig. 3 shows that the titanizing metal level is transformed into Jie at the phase titanium coating through behind the annealing heat treatment operation.Extremely shown in Figure 3 like Fig. 1; When making the nano-tube shaped solar battery thin film of array of the present invention; Must prepare together sensing type (Isotropy) silicon substrate 1 earlier, in this manual, so-calledly be meant that with the sensing type its surface crystallization is to arrange with identical sensing.In addition, can be together sensing type silicon garden sheet (Silicon Wafer) with sensing type silicon substrate 1, also can serve as reasons cuts the same sensing type silicon that forms with sensing type silicon garden sheet.
Then, an electricity slurry vapour deposition (Plasma Vapor Deposition capable of using; PVD) equipment carries out a sputter operation, so as to going out a titanizing metal level 2 at the surperficial sputter with sensing type silicon substrate 1, makes with sensing type silicon substrate 1 and titanizing metal level 2 and forms a titanizing silicon substrate 100.Then, can in a vacuum heat environment, carry out a vacuum heat operation, so as to eliminating titanizing metal level 2 and, making titanizing metal level 2 and be able to closely combine with sensing type silicon substrate 1 with the residual stress of 1 of sensing type silicon substrate to titanizing silicon substrate 100.Wherein, the pressure of vacuum heat environment can be set at 0.01torr, and the temperature of vacuum heat environment can be set at 920 ℃.
And then, can in an annealing heat treatment environment, carry out an annealing heat treatment operation, make titanizing metal level 2 be transformed into one and be situated between at phase titanium coating 2a to titanizing silicon substrate 100.In this preferred embodiment, the temperature of annealing heat treatment environment can be 850 ℃, and the annealing heat treatment operation can be kept 1 hour.Simultaneously, Jie mainly can be made up of the sharp ore deposit of titanium dioxide type (anatase phase) crystalline texture at phase titanium coating 2a.
After accomplishing the annealing heat treatment operation, an electrobrightening capable of using (Electrolytic Polishing) operation is cleaned and is polished the titanizing metal level.When the electrobrightening operation; Be will be situated between to be positioned over anode tap together with above-mentioned same sensing type silicon substrate 1 at phase titanium coating 2a, and with a platinum electrode as cathode terminal, in electrolyte, switch on; Under suitable operating parameter; Make Jie cell reaction (also claiming anti-the plating) take place, produce dissolution on the surface of phase titanium coating 2a because of the electric field concentration effect so as to making Jie, so as to making the flattening surface and the glossization of Jie at phase titanium coating 2a at phase titanium coating 2a.
When carrying out above-mentioned electrobrightening operation, the modulation prescription of electrolyte comprises: cross chloric acid (Perchloric Acid; HClO
4), ethylene glycol monobutyl ether (Ethylene Glycol Monobutyl-ether; HOCH
2CH
2OC
4H
9) and methyl alcohol (Methanol; CH
3OH), and the temperature of electrolyte be 15 ℃.In the present embodiment, the electrobrightening operating voltage suggestion when carrying out above-mentioned electrobrightening operation was kept 1 minute for applying 52 volts earlier, then changed 28 volts into and kept 13 minutes.
Next, must carry out an anode treatment operation at phase titanium 2a to being situated between; At this moment, must will be situated between and immerse in the electrolyte, and apply an operating voltage at phase titanium coating 2a.Preferably; When carrying out above-mentioned anode treatment operation; Can utilize an electrochemistry direct current polarization curved scanning (Electrochemistry DC Polarization Curve Scanning) operation earlier; Assess out an optimization operational voltage value of above-mentioned operating voltage and an optimization electrolyte pH-value (pH value) of above-mentioned electrolyte, apply above-mentioned operating voltage according to the optimization operational voltage value, and according to optimization electrolyte pH-value modulation electrolyte.
In the preferable enforcement of the present invention, when the area of titanizing silicon substrate 100 is 2cm * 2cm, can above-mentioned optimization operational voltage value be set at 10 volts (V) to 20V, wherein preferable with 15V, reason please be considered Fig. 5 D in light of actual conditions.Simultaneously, can be according to optimization electrolyte pH-value, make hydrofluoric acid (the Hydrofluoric Acid that comprises 1.2vol.% (concentration expressed in percentage by volume) in the modulation prescription of electrolyte; HF) and the sulfuric acid of 10vol.% (Sulfuric Acid; H
2SO
4) wait raw material.
See also Fig. 4 to Fig. 5 G; Wherein Fig. 4 is presented at being situated between after the phase titanium coating carries out the anode treatment operation; Make Jie be transformed into the nano-tube shaped solar battery thin film of array at the phase titanium coating; Fig. 5 A to Fig. 5 G is presented under the different operating voltages, and the nano-tube shaped solar battery thin film of formed array is institute's images displayed under electron microscope.As shown in Figure 4, to being situated between after phase titanium coating 2a accomplishes the anode treatment operation, can make Jie be transformed into the nano-tube shaped solar battery thin film 2b of an array at phase titanium coating 2a.In the nano-tube shaped solar battery thin film 2b of array, comprise a titanium dioxide base film layer 21b and a plurality of titania nanotube 22b that arranges with a closely spaced array (Concentrated Array).
In this enforcement, shown in Fig. 5 A, when the operating voltage that is applied is 10V, from electron microscope show multiplying power reach 80,000 times time institute's images displayed, titania nanotube has begun to appear large-scale growth.
Shown in Fig. 5 B, when the operating voltage that is applied is promoted to 12V, from electron microscope show multiplying power reach 80,000 times time institute's images displayed, the growth of titania nanotube is shaped gradually.
Shown in Fig. 5 C, when the operating voltage that is applied is promoted to 13V, from electron microscope show multiplying power reach 30,000 times time institute's images displayed, titania nanotube is expanded once again.
Shown in Fig. 5 D, when the operating voltage that is applied is promoted to 15V, from electron microscope show multiplying power reach 30,000 times time institute's images displayed, titania nanotube is quite intensive and arrange regularly with a closely spaced array.
Shown in Fig. 5 E; When the operating voltage that is applied is promoted to 16V; From electron microscope show multiplying power reach 80,000 times time institute's images displayed; Titania nanotube is still kept with closely spaced array quite intensive and arrange regularly, but the titania nanotube of existing part has begun to have the slight phenomenon that collapses to take place.
Shown in Fig. 5 F, when the operating voltage that is applied is promoted to 18V, from electron microscope show multiplying power reach 80,000 times time institute's images displayed, the titania nanotube phenomenon that collapses continues to take place, titania nanotube partly begins distortion.
Shown in Fig. 5 G; When the operating voltage that is applied is promoted to 20V; From electron microscope show multiplying power reach 80,000 times time institute's images displayed, the titania nanotube phenomenon that collapses continues to take place titania nanotube distortion aggravation partly; And the mouth of pipe of titania nanotube begins to merge, and on the mouth of pipe of titania nanotube, begins to occur a large amount of sediments.Can know that by Fig. 5 A to Fig. 5 G in preferred embodiment of the present invention, when the area of titanizing silicon substrate 100 was 2cm * 2cm, above-mentioned optimization operational voltage value should be preferable with 15V.
See also Fig. 6, after it was presented at and applies a revers voltage, the nano-tube shaped solar battery thin film of array was from breaking away from sensing type silicon substrate.As shown in Figure 6; Be situated between after phase titanium coating 2a is transformed into the nano-tube shaped solar battery thin film 2b of array; Can apply a revers voltage (the operating voltage voltage in the opposite direction when carrying out the anode treatment operation), make the nano-tube shaped solar battery thin film 2b of array from breaking away from sensing type silicon substrate 1.
Please continue to consult Fig. 7, one of them titanium dioxide unit structure of its displayed map 6.As shown in Figure 6, a titanium dioxide unit structure comprises the titanium dioxide base film layer 21b of a titania nanotube 22b (to single titania nanotube 22b, can abbreviate test-tube baby as again) bottom it.Wherein, each titania nanotube 22b on average takies the average occupied area of a unit (zone of titanium dioxide base film layer 21b as shown in Figure 6) of titanium dioxide base film layer 21b, and the average occupied area of unit has a unit and on average takies surface area A0.Titania nanotube 22b has a bore Ri, an external diameter of pipe Ro and a pipe range L; Simultaneously; Titania nanotube 22b comprises a bottom surface 221b, an end face 222b, an internal face 223b and an outside wall surface 224b, and bottom surface 221b, end face 222b, internal face 223b and outside wall surface 224b have a base area A1, a top surface area A2, an internal face area A 3 and an outside wall surface area A 4 respectively.Because titania nanotube 22b is grown the structure that both are formed in one by titanium dioxide base film layer 21b; Therefore, bottom surface 221b does not expose, and has only end face 222b, internal face 223b can expose with light-sensitive coloring agent with outside wall surface 224b and contacts.
Can know that by Fig. 7 if positive plate do not have titania nanotube 22b fully, as far as an average occupied area of unit, can only the unit of providing on average take surface area A0 and contact with light-sensitive coloring agent, in other words, its contact area has only unit on average to take surface area A0.Yet; When positive plate has the nano-tube shaped solar battery thin film 2b of above-mentioned array; If it is more little that the unit of the average occupied area of unit that each titania nanotube 22b is shared on average takies surface area A0, the titania nanotube 22b that expression is arranged with above-mentioned closely spaced array distributes intensively more.
In addition; When the nano-tube shaped solar battery thin film 2b of array is made into the positive plate of (dye sensitization) solar cell; To each titanium dioxide unit structure; On average take surface area A0-base area A1+ top surface area A2+ internal face area A 3+ outside wall surface area A 4 with the effective contact area unit of should be of light-sensitive coloring agent, in other words, its contact area=unit on average takies surface area A0-base area A1+ top surface area A2+ internal face area A 3+ outside wall surface area A 4.Because base area A1 is very close with top surface area A2, so its contact area=unit on average takies surface area A0+ internal face area A 3+ outside wall surface area A 4.In other words; Compared to the positive plate that does not have titania nanotube 22b fully; To each titanium dioxide unit structure; Effective contact area according to nano-tube shaped solar battery thin film 2b of the produced array of the present invention and light-sensitive coloring agent can increase internal face area A 3+ outside wall surface area A 4, promptly increases by 2 * π * Ri * L+2 * π * Ro * L.
Hence one can see that, and effective contact area of nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent is on average to take surface area A0 with unit and pipe range L is closely bound up.When unit on average takies the more little or pipe range L of surface area A0 when long more, effective contact area of nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent is big more.
Figure can know via composition element depth profiles, and in an embodiment of the present invention, when operating voltage was 10V, the pipe range of titania nanotube was about 2.52 microns (μ m); When operating voltage was 15V, the pipe range of titania nanotube was about 5.4 μ m; When operating voltage was 10V, the pipe range of titania nanotube was about 6.12 μ m.Yet; Consulting Fig. 5 G simultaneously can know; Though when the operating voltage that is applied was promoted to 20V, the pipe range of titania nanotube can reach about 6.12 μ m, phenomenon continues to take place because titania nanotube collapses; Titania nanotube distortion aggravation partly; And the mouth of pipe of titania nanotube begins to merge, and on the mouth of pipe of titania nanotube, begins to occur a large amount of unfavorable factors such as sediment, will reduce effective contact area of nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent.Judge comprehensively that by above factor in preferred embodiment of the present invention, preferable operating voltage should be 15V.
Dense arrangement property about titania nanotube; Owing to can't directly obtain the laboratory sample of known ' No. 538 patent case; So the experimental result that can only be disclosed to Fig. 5 A of known ' No. 538 patent specification is compared with the nano-tube shaped solar battery thin film 2b of array shown in Fig. 5 D of the present invention.Fig. 5 A of ' No. 538 patent specification can know by known; In the area of positive plate surface 500nm * 500nm; 36 titania nanotubes of conformal written treaty are so can learn that known unit on average takies surface area and is about 7000 square nanometers in No. 538 patent case of '.Yet can know by the graphic rabbit 5D of the present invention; In the area of the nano-tube shaped solar battery thin film 2b of array surface 500nm * 500nm; 43 to 45 titania nanotubes of conformal written treaty; So can learn that in preferred embodiment of the present invention above-mentioned unit on average takies surface area A0 and is about 5600 square nanometers to 5800 square nanometers.
Can know from above narration; Because as far as each titanium dioxide unit structure; Unit of the present invention on average takies surface area A0 and has only 5600 square nanometers to 5800 square nanometers approximately; Approximately have only ' No. 538 revealer's of patent case institute 80% known, obvious in the nano-tube shaped solar battery thin film 2b of the array that utilizes made of the present invention, the dense arrangement property of titania nanotube is more known, and ' No. 538 patent case person is good.
In addition, in many scholar experts' correlative study, also fully prove: if the directive property more regular (promptly more consistent) of titanium, when it formed titania nanotube via anode treatment, it is long that the titania nanotube that is generated can have longer pipe.Because the titanium sprayed coating that is disclosed in No. 538 patent specification of ' known is to be shaped with spraying method; Its surperficial crystal boundary arrangement is pointed to quite chaotic and irregular; So the sensing of the titania nanotube that is generated is also quite irregular, causes the pipe range of its titania nanotube shorter; Yet; In the present invention, owing to be to utilize with sensing type silicon substrate 1, and utilize sputtering way to form titanizing metal level 2; Therefore; After in regular turn through above-mentioned vacuum heat operation, annealing heat treatment operation and anode treatment operation, among the nano-tube shaped solar battery thin film 2b of the array that is generated, the arrangement directive property of titania nanotube 22b is also comparatively regular; Hence one can see that, utilizes the titania nanotube 22b of the nano-tube shaped solar battery thin film 2b of the produced array of the present invention to have the long L of longer pipe.
Can know by above narration; ' No. 538 patent compared to known; Because in the nano-tube shaped solar battery thin film 2b of technological produced array that utilizes the present invention to disclose; As far as each titanium dioxide unit structure, it is more little that unit on average takies surface area A0, and the pipe range of titania nanotube 22b is longer; Obviously, utilize effective contact area of nano-tube shaped solar battery thin film 2b of the produced array of the present invention and light-sensitive coloring agent can be more known ' No. 538 patent for big.
At last, please continue to consult Fig. 8, it shows the simple making method flow chart of the nano-tube shaped solar battery thin film of array that preferred embodiment of the present invention disclosed.As shown in Figure 8, when making the nano-tube shaped solar battery thin film 2b of array, preparation is with sensing type silicon substrate 1 (step 110) earlier; And go out titanizing metal level 2 at surperficial sputter with sensing type silicon substrate 1, form titanizing silicon substrates 100 (steps 120) so as to making with sensing type silicon substrate 1 and titanizing metal level 2.Then; Must titanizing silicon substrate 100 be positioned over and carry out the vacuum heat operation in the vacuum heat environment; So as to eliminating titanizing metal level 2 and with the residual stress (step 130) of 1 of sensing type silicon substrate; And titanizing silicon substrate 100 is positioned over the annealing heat treatment operation of annealing in the heat treatment environment, be transformed into Jie at phase titanium coating 2a (step 140) so as to making titanizing metal level 2.
And then; Electrobrightening operation cleaning capable of using and polishing titanizing metal level 2 (steps 150); Electrochemistry direct current polarization curved scanning capable of using operation; Assess out optimization operational voltage value (step 160) to Jie's required operating voltage that applies when phase titanium coating 2a carries out the anode treatment operation; Simultaneously, the optimization electrolyte pH-value (step 170) to Jie's electrolyte of required immersion when phase titanium coating 2a carries out the anode treatment operation is assessed out in electrochemistry direct current polarization curved scanning more capable of using operation.
Then; Apply operating voltage according to the optimization operational voltage value; According to optimization electrolyte pH-value allotment electrolyte; So as to carrying out the anode treatment operation at phase titanium coating 2a, make Jie be transformed into the nano-tube shaped solar battery thin film 2b of array, and the surface of the nano-tube shaped solar battery thin film 2b of array have a plurality of titania nanotube 22b (step 180) that arrange with closely spaced array at phase titanium coating 2a to being situated between.At last, apply revers voltage, make the nano-tube shaped solar battery thin film 2b of array from breaking away from (step 190), for making DSSC (Dye-Sensitized Solar Cell with sensing type silicon substrate 1; The usefulness of positive plate DSSC).
Such as those skilled in the art; No matter be via experiment proof or qualitative analysis; All be appreciated that; In the present invention and since be with same sensing type silicon substrate 1 with single arrangement directive property as base material, and utilize the mode of sputter to make to be coated on and starve titanizing metal level 2 with the surface of sensing type silicon substrate and have higher causes such as Ti content; Therefore, the surface of the nano-tube shaped solar battery thin film 2b of produced array has a plurality of titania nanotube 22b that arrange with closely spaced array, and makes titania nanotube 22b have long length.
By this, can make the titanium dioxide (comprising titanium dioxide base film layer 21b and titania nanotube 22b) on the nano-tube shaped solar battery thin film 22b of array surface have bigger surface area.Therefore; When utilizing the nano-tube shaped solar battery thin film 2b of the produced array of the present invention to come the positive plate of manufacturing solar cells; Can make between surperficial titanium dioxide of the nano-tube shaped solar battery thin film 2b of array and the light-sensitive coloring agent and have bigger contact area; So as to promoting the photoelectric conversion efficiency of solar cell, and then obtain to supply human use's electric energy more efficiently.
Certainly; The present invention also can have other various embodiments; Under the situation that does not deviate from spirit of the present invention and essence thereof; Those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (11)
1. the manufacture method of the nano-tube shaped solar battery thin film of array is characterized in that, comprises following steps:
(a) prepare together sensing type silicon substrate;
(b) go out a titanizing metal level to form a titanizing silicon substrate at this surperficial sputter with sensing type silicon substrate;
(c) this titanizing silicon substrate is positioned over carries out a vacuum heat operation in the vacuum heat environment, so as to eliminating this titanizing metal level and should be with the residual stress between sensing type silicon substrate;
(d) this titanizing silicon substrate is positioned over an annealing and carries out an annealing heat treatment operation in the heat treatment environment, be situated between at the phase titanium coating so as to making this titanizing metal level be transformed into one;
(e) this Jie is carried out an anode treatment operation at the phase titanium coating; So as to making this Jie be transformed into the nano-tube shaped solar battery thin film of this array at the phase titanium coating, and the surface of the nano-tube shaped solar battery thin film of this array has a plurality of titanium dioxide (TiO that arrange with a closely spaced array
2) nanotube; And
(f) apply a revers voltage, make the nano-tube shaped solar battery thin film of this array from breaking away from sensing type silicon substrate.
2. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, this is together sensing type silicon garden sheet with sensing type silicon substrate.
3. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, this Jie mainly is made up of the sharp ore deposit of titanium dioxide type crystalline texture at the phase titanium coating.
4. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, this step (b) utilizes an electricity slurry vapor deposition apparatus to carry out.
5. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, in this step (c), the pressure of this vacuum heat environment is 0.01torr, and the temperature of this vacuum heat environment is 920 ℃.
6. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 5 is characterized in that, in this step (d), the temperature of this annealing heat treatment environment is 850 ℃, and this annealing heat treatment operation was kept 1 hour.
7. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, in the preceding step (e0) that more comprises of this step (e), it is cleaning and polishes this titanizing metal level.
8. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 7 is characterized in that, this step (e0) is to utilize an electrobrightening operation to accomplish.
9. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1 is characterized in that, in this step (e), is that this Jie is immersed in the electrolyte at the phase titanium coating, and applies an operating voltage, so as to carrying out this anode treatment operation.
10. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 9; It is characterized in that; In this step (e), more comprise a step (e1); It is to utilize an electrochemistry direct current polarization curved scanning operation, assesses out an optimization operational voltage value of this operating voltage and an optimization electrolyte pH-value of this electrolyte.
11. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 10; It is characterized in that; In this step (e1); When the area of this titanizing silicon substrate was 2cm * 2cm, this optimization operational voltage value was 10V to 20V, and comprises the hydrofluoric acid of 1.2vol.% and the sulfuric acid of 10vol.% in the modulation of this electrolyte prescription.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740406A (en) * | 2004-08-28 | 2006-03-01 | 清华大学 | Nanometer silicon wire structure and its growth process |
| JP2007070136A (en) * | 2005-09-05 | 2007-03-22 | Kyoto Univ | Titania nano-rod, its manufacture method, and dye sensitizing solar battery using this titania nano-rod |
| CN101447341A (en) * | 2008-12-30 | 2009-06-03 | 南京航空航天大学 | Flexible dye-sensitized solar battery with stainless steel as substrate and preparation method thereof |
| US20100044630A1 (en) * | 2008-08-20 | 2010-02-25 | Korea Advanced Institute Of Science And Technology | TiO2-xNx Nanotubes and Method for Preparing the Same |
| TW201010108A (en) * | 2008-08-26 | 2010-03-01 | Dc Solar Corp | Large area dye-sensitized solar cell and the thermal spraying fabrication methods thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740406A (en) * | 2004-08-28 | 2006-03-01 | 清华大学 | Nanometer silicon wire structure and its growth process |
| JP2007070136A (en) * | 2005-09-05 | 2007-03-22 | Kyoto Univ | Titania nano-rod, its manufacture method, and dye sensitizing solar battery using this titania nano-rod |
| US20100044630A1 (en) * | 2008-08-20 | 2010-02-25 | Korea Advanced Institute Of Science And Technology | TiO2-xNx Nanotubes and Method for Preparing the Same |
| TW201010108A (en) * | 2008-08-26 | 2010-03-01 | Dc Solar Corp | Large area dye-sensitized solar cell and the thermal spraying fabrication methods thereof |
| CN101447341A (en) * | 2008-12-30 | 2009-06-03 | 南京航空航天大学 | Flexible dye-sensitized solar battery with stainless steel as substrate and preparation method thereof |
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