CN102403130B - Method for manufacturing array nano tube type solar cell thin film - Google Patents
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- CN102403130B CN102403130B CN201010277037.0A CN201010277037A CN102403130B CN 102403130 B CN102403130 B CN 102403130B CN 201010277037 A CN201010277037 A CN 201010277037A CN 102403130 B CN102403130 B CN 102403130B
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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, about a kind of manufacture method of solar battery thin film, refers to a kind of manufacture method of utilizing the nano-tube shaped solar battery thin film of array of silicon wafer manufacture especially.
Background technology
Look about the residing living environment of current masses, due to industrial expansion, the global energy is consumed just rapidly.By many scholar's expert investigations survey report out, the mankind come to realise gradually and oneself are at present energy critical shortage Key Years generation, and global various countries competitively develop the pollution-free and callable renewable energy resources invariably.According to the estimation of american energy office, from 2003, to start at, the irreproducibility energy of oil, natural gas and coal etc. will be exhausted respectively in 41 years, 67 years and 192 years.Under these circumstances, the exploitation of the 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, due to solar energy, to have power generation process pollution-free and without the characteristic of standing charges, so be generally subject to 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 one after another to carry out new forms of energy policy, and implements subsidy incentive method, in the hope of develop actively with promote solar cell.
According to expert's statistical result showed, the energy that the sun is radiated to the earth is every year about 5.4 * 10
24joule, and the annual required energy in the whole world is about 1.1 * 10
20joule; Therefore, if the mankind can utilize fully 50,000 of energy from solar radiation to the earth/, current the faced many energy problems of the mankind just can be readily solved at once.In view of this, be necessary that 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 mankind can extend to the microcosmos of nanometer gradually to the grasp of the physical structure of various materials and chemical characteristic.In recent years, because part expert is actively by the field that is introduced into solar cell of nanometer technology, allow especially the manufacturing technology of solar cell and usefulness produce revolutionary important breakthrough, make solar product can meet the user demand of people's livelihood articles for use gradually.
Review to calendar year 2001, solar power generation amount only accounts for 0.1% of global power consumption, and solar energy industry is with annual 35～40% speed Sustainable Growth.Yet by 2005, global photovoltaic (Photovoltaic) total installation of generating capacity reached 2200 megavolts, approximately 3,000,000,000 thousand watts-hour of annual energy outputs.Estimated for the end of the year 2010, the scale in global solar photoelectric market will be over 50,000,000,000 dollars.
Further discuss, the kind of current 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 propose the solar energy manufacturing technology of multiple titanium dioxide (TiO2) film, particle and nanotube (NT, nanotubes) in succession.
The TaiWan, China patent 097132538(of take application) number (patent name is " large-area dye-sensitized solar battery and hot melt thereof are penetrated and sprayed manufacture method ", 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 thereon
2) nanotube, the anode of usining as battery; Light-sensitive coloring agent, is adsorbed in the surface of titania nanotube; Transparent conductive cathode, arranges 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 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 titanium sprayed coating, then titanium sprayed coating is carried out anode processing and heat treatment and is formed.
Processing about the positive plate of solar cell, comprises following steps: with hot melt, penetrate spraying process titanium is sprayed on the surface of base material, and produce titanium sprayed coating; Then titanium sprayed coating is carried out to anode processing 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, 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.In the disclosed technology of ' No. 538 Patent Case known, base material does not possess arrangement directive property, and is easily mixed with impurity during titanium and makes the causes 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.
In order to improve photoelectric conversion efficiency, this case inventor thinks and is necessary to develop a kind of manufacturing technology of the new nano-tube shaped solar battery thin film of array, so as to increasing length and the distribution density of the titania nanotube of the nano-tube shaped solar battery thin film of array, phase can, when utilizing the nano-tube shaped solar battery thin film of this array to make positive plate, effectively increase the contact area of light-sensitive coloring agent and titanium dioxide.
Summary of the invention
Technical problem and object that institute of the present invention wish solves:
Take a broad view of the above, in known technology, particularly known in the disclosed technology of ' No. 538 Patent Case, because base material does not possess arrangement directive property, and when spraying titanium, be easily mixed with impurity and make the causes 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, more can therefore produce the problem of the contact area deficiency 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, be wherein to using a same directing silicon substrate with single arrangement directive property as base material, and utilize the mode of sputter to make the surperficial titanizing metal level that is coated on same directing silicon substrate there is higher Ti content.By this, can make the surface of the produced nano-tube shaped solar battery thin film of array there are a plurality of titania nanotubes of arranging with a closely spaced array, and make titania nanotube there is longer length.
The technological means that the problem that the present invention is solution known technology adopts is to provide the manufacture method of the nano-tube shaped solar battery thin film of a kind of array, this manufacture method is first to prepare together directing silicon substrate, and goes out a titanizing metal level to form a titanizing silicon substrate at the surperficial sputter of same directing silicon substrate.Then, in a vacuum heat environment, titanizing silicon substrate is carried out to a vacuum heat operation, so as to elimination titanizing metal level and with the residual stress between directing silicon substrate, and continue, in an annealing heat treatment environment, titanizing silicon substrate is carried out to an annealing heat treatment operation, make titanizing metal level be transformed into Jie at phase titanium coating, wherein, this Jie is mainly comprised of the sharp ore deposit of titanium dioxide type crystalline texture at phase titanium coating.Then, to being situated between, at phase titanium coating, carry out an anode processing operation, so as to making to be situated between, at phase titanium coating, be transformed into the nano-tube shaped solar battery thin film of array, make its surface there are a plurality of titanium dioxide (TiO that arrange with a closely spaced array
2) nanotube.Finally, apply a revers voltage, make the nano-tube shaped solar battery thin film of array from departing from directing silicon substrate.
Preferably, be situated between and mainly can be formed by the sharp ore deposit of titanium dioxide type (anatase phase) crystalline texture at phase titanium coating; Above-mentioned same directing silicon substrate can be together directing silicon wafer; The operation that goes out a titanizing metal level at the surperficial sputter of same directing silicon substrate can utilize an electricity slurry vapour deposition (Plasma Vapor Deposition; 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 annealing heat treatment operation can maintain 1 hour.
To being situated between before phase titanium coating carries out an anode processing operation, can utilize an electrobrightening (Electrolytic Polishing) operation to be cleaned and polishing titanizing metal level.When carrying out above-mentioned anode processing operation, be that Jie is immersed in an electrolyte at phase titanium coating, and apply an operating voltage.Preferably, when carrying out above-mentioned anode processing operation, can first utilize an electrochemistry direct current polarization curved scanning (Electrochemistry DC Polarization Curve Scanning) operation, evaluate an optimization operational voltage value of above-mentioned operating voltage and an optimization electrolyte pH-value of above-mentioned electrolyte, according to optimization operational voltage value, apply above-mentioned operating voltage, and according to optimization electrolyte pH-value modulation electrolyte.
In addition, in the better enforcement of the present invention, when the area of titanizing silicon substrate is 2cm * 2cm, above-mentioned optimization operational voltage value can be set as to 10V to 20V, and can be according to optimization electrolyte pH-value, make to comprise 1.2vol.%(concentration expressed in percentage by volume in the modulation formula of electrolyte) hydrofluoric acid (Hydrofluoric Acid; HF) and the sulfuric acid of 10vol.% (Sulfuric Acid; H
2sO
4) etc. raw material.
Beneficial functional of the present invention is, compared to utilizing the produced dye sensitized solar battery anode plate of known technology, although its surface also has titania nanotube, but because base material does not possess arrangement directive property, and be easily mixed with impurity during titanium and make the causes 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, via experimental results show that or qualitative analysis known, in the present invention, because being has the same directing silicon substrate of single arrangement directive property as base material, and utilize the mode of sputter to make the surperficial titanizing metal level that is coated on same directing silicon substrate there is the higher causes such as Ti content; 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 longer 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 there is larger surface area.When utilizing the nano-tube shaped solar battery thin film of the produced array of the present invention to make solar battery anode plate, can make to there is larger contact area between the titanium dioxide on the nano-tube shaped solar battery thin film of array surface and light-sensitive coloring agent, so as to promoting the photoelectric conversion efficiency of solar cell, and then obtain more efficiently the electric energy that can supply human use.
Below in conjunction with the drawings and specific embodiments, describe the present invention, but not as a limitation of the invention.
Accompanying drawing explanation
Fig. 1 shows together directing silicon substrate;
Fig. 2 demonstration utilizes a sputter operation, at same directing silicon substrate, plates titanizing metal level to form titanizing silicon substrate;
Fig. 3 demonstration is after an annealing heat treatment operation, and titanizing metal level is transformed into Jie at phase titanium coating;
Fig. 4 is presented at and carries out after anode processing operation at phase titanium coating being situated between, and making to be situated between is transformed into the nano-tube shaped solar battery thin film of array at phase titanium coating;
Fig. 5 A to Fig. 5 G is presented under different operating voltages, the nano-tube shaped solar battery thin film of formed array shown image under electron microscope;
Fig. 6 is presented at and applies after a revers voltage, and the nano-tube shaped solar battery thin film of array is from departing from directing silicon substrate;
Fig. 7 shows one of them titanium dioxide unit structure of Fig. 6; And
Fig. 8 shows the simple making method flow chart of the nano-tube shaped solar battery thin film of the disclosed array of preferred embodiment of the present invention.
Wherein, Reference numeral
100 titanizing silicon substrates
1 with directing silicon substrate
2 titanizing metal levels
2a is situated between at phase titanium coating
The nano-tube shaped solar battery thin film of 2b array
21b titanium dioxide base film layer
22b titania nanotube
221b bottom surface
222b end face
223b internal face
224b outside wall surface
Ri bore
Ro manages external diameter
L pipe range
A0 unit on average takies surface area
A1 base area
A2 top surface area
A3 internal face area
A4 outside wall surface area
Embodiment
Below in conjunction with the drawings and specific embodiments, technical solution of the present invention being described in detail, further to understand object of the present invention, scheme and effect, but is not the restriction as claims protection range of the present invention.
Due to 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, be particularly applied to make DSSC (Dye-Sensitized Solar Cell; DSSC) positive plate, its combination execution mode is too numerous to enumerate especially, therefore this is no longer going to repeat them, only enumerates one of them preferred embodiment and is illustrated, and quote relevant experimental result and verify aforesaid effect.
Refer to Fig. 1 to Fig. 3, wherein, Fig. 1 shows together directing silicon substrate; Fig. 2 demonstration utilizes a sputter operation, at same directing silicon substrate, plates titanizing metal level to form titanizing silicon substrate; And Fig. 3 shows after an annealing heat treatment operation, titanizing metal level is transformed into and is situated between at phase titanium coating.As shown in Figure 1 to Figure 3, when making the nano-tube shaped solar battery thin film of array of the present invention, must first prepare together directing (Isotropy) silicon substrate 1, in this manual, so-called same directing refers to that its surface crystallization is arranged with identical sensing.In addition, with directing silicon substrate 1, can be together directing silicon wafer (Silicon Wafer), the same directing silicon wafer of also can serving as reasons cuts the same directing silicon forming.
Then, can utilize an electricity slurry vapour deposition (Plasma Vapor Deposition; PVD) equipment carries out a sputter operation, so as to the surperficial sputter at same directing silicon substrate 1, goes out a titanizing metal level 2, makes same directing silicon substrate 1 and titanizing metal level 2 form a titanizing silicon substrate 100.Then, can in a vacuum heat environment, to titanizing silicon substrate 100, carry out a vacuum heat operation, so as to eliminating titanizing metal level 2 and with the residual stress of 1 of directing silicon substrate, titanizing metal level 2 being closely combined with same directing silicon substrate 1.Wherein, the pressure of vacuum heat environment can be set as 0.01torr, and the temperature of vacuum heat environment can be set as 920 ℃.
And then, can in an annealing heat treatment environment, to titanizing silicon substrate 100, carry out an annealing heat treatment operation, make titanizing metal level 2 be transformed into Jie at phase titanium coating 2a.In this preferred embodiment, the temperature of annealing heat treatment environment can be 850 ℃, and annealing heat treatment operation can maintain 1 hour.Meanwhile, be situated between and mainly can be formed by the sharp ore deposit of titanium dioxide type (anatase phase) crystalline texture at phase titanium coating 2a.
After completing annealing heat treatment operation, can utilize an electrobrightening (Electrolytic Polishing) operation to be cleaned and polishing titanizing metal level.When electrobrightening operation, at phase titanium coating 2a, together with above-mentioned same directing silicon substrate 1, to be positioned over anode tap by being situated between, and using a platinum electrode as cathode terminal, in electrolyte, switch on, under suitable operating parameter, making to be situated between there is cell reaction (also claiming anti-plating) at phase titanium coating 2a, so as to making to be situated between on the surface of phase titanium coating 2a because electric field concentration effect produces dissolution, so as to flattening surface and the glossing that makes to be situated between at phase titanium coating 2a.
When carrying out above-mentioned electrobrightening operation, the modulation formula 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 while carrying out above-mentioned electrobrightening operation maintains 1 minute for first applying 52 volts, then changes 28 volts into and maintains 13 minutes.
Next, must at phase titanium 2a, carry out an anode processing operation to being situated between; Now, must at phase titanium coating 2a, immerse in an electrolyte being situated between, and apply an operating voltage.Preferably, when carrying out above-mentioned anode processing operation, can first utilize an electrochemistry direct current polarization curved scanning (Electrochemistry DC Polarization Curve Scanning) operation, evaluate an optimization operational voltage value of above-mentioned operating voltage and an optimization electrolyte pH-value (pH value) of above-mentioned electrolyte, according to optimization operational voltage value, apply above-mentioned operating voltage, and according to optimization electrolyte pH-value modulation electrolyte.
In the better enforcement of the present invention, when the area of titanizing silicon substrate 100 is 2cm * 2cm, above-mentioned optimization operational voltage value can be set as to 10 volts (V) to 20V, wherein better with 15V, reason please be considered Fig. 5 D in light of actual conditions.Meanwhile, can be according to optimization electrolyte pH-value, make to comprise 1.2vol.%(concentration expressed in percentage by volume in the modulation formula of electrolyte) hydrofluoric acid (Hydrofluoric Acid; HF) and the sulfuric acid of 10vol.% (Sulfuric Acid; H
2sO
4) etc. raw material.
Refer to Fig. 4 to Fig. 5 G, wherein Fig. 4 is presented at and carries out after anode processing operation at phase titanium coating being situated between, make to be situated between and be transformed into the nano-tube shaped solar battery thin film of array at phase titanium coating, Fig. 5 A to Fig. 5 G is presented under different operating voltages, the nano-tube shaped solar battery thin film of formed array shown image under electron microscope.As shown in Figure 4, to being situated between, at phase titanium coating 2a, complete after anode processing operation, can make to be situated between is 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 arranging with a closely spaced array (Concentrated Array).
In this enforcement, as shown in Figure 5A, when applied operating voltage is 10V, shown image while showing that from electron microscope multiplying power reaches 80,000 times, titania nanotube has started to present large-scale growth.
As shown in Figure 5 B, when applied operating voltage is promoted to 12V, shown image while showing that from electron microscope multiplying power reaches 80,000 times, the growth of titania nanotube is shaped gradually.
As shown in Figure 5 C, when applied operating voltage is promoted to 13V, shown image while showing that from electron microscope multiplying power reaches 30,000 times, titania nanotube is expanded once again.
As shown in Figure 5 D, when applied operating voltage is promoted to 15V, shown image while showing that from electron microscope multiplying power reaches 30,000 times, titania nanotube is quite intensive and arrange regularly with a closely spaced array.
As shown in Fig. 5 E, when applied operating voltage is promoted to 16V, shown image while showing that from electron microscope multiplying power reaches 80,000 times, it is quite intensive and arrange regularly with closely spaced array that titania nanotube still maintains, but the titania nanotube of existing part has started to have the slight phenomenon that collapses to occur.
As shown in Fig. 5 F, when applied operating voltage is promoted to 18V, shown image while showing that from electron microscope multiplying power reaches 80,000 times, the titania nanotube phenomenon that collapses continues to occur, and the titania nanotube of part starts distortion.
As shown in Fig. 5 G, when applied operating voltage is promoted to 20V, shown image while showing that from electron microscope multiplying power reaches 80,000 times, titania nanotube collapses, and phenomenon is lasting to be occurred, the titania nanotube distortion aggravation of part, and the mouth of pipe of titania nanotube starts to merge, and on the mouth of pipe of titania nanotube, starts to occur a large amount of sediments.From Fig. 5 A to Fig. 5 G, in preferred embodiment of the present invention, when the area of titanizing silicon substrate 100 is 2cm * 2cm, above-mentioned optimization operational voltage value should be better with 15V.
Refer to Fig. 6, it is presented at and applies after a revers voltage, and the nano-tube shaped solar battery thin film of array is from departing from directing silicon substrate.As shown in Figure 6, Jie, at phase titanium coating 2a, be transformed into after the nano-tube shaped solar battery thin film 2b of array, can apply a revers voltage (voltage of the operating voltage opposite direction when carrying out anode processing operation), make the nano-tube shaped solar battery thin film 2b of array from departing from directing silicon substrate 1.
Please continue to refer to Fig. 7, it shows one of them titanium dioxide unit structure of Fig. 6.As shown in Figure 6, a titanium dioxide unit structure comprises a titania nanotube 22b(for single titania nanotube 22b, again can be referred to as test-tube baby) with the titanium dioxide base film layer 21b of its bottom.Wherein, each titania nanotube 22b on average takies an average occupied area of unit (region 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, pipe external diameter 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 respectively a base area A1, a top surface area A2, an internal face area A 3 and an outside wall surface area A 4.Because titania nanotube 22b is grown by titanium dioxide base film layer 21b, the structure that both are formed in one; Therefore, bottom surface 221b does not expose, and only has end face 222b, internal face 223b can expose with light-sensitive coloring agent and contact with outside wall surface 224b.
As shown in Figure 7, if positive plate does not have titania nanotube 22b completely, the average occupied area of Dui Yige unit, can only the unit of providing on average takies surface area A0 and contacts with light-sensitive coloring agent, and in other words, its contact area only has 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 less that the unit of the average occupied area of unit that each titania nanotube 22b is shared on average takies surface area A0, represent that the titania nanotube 22b arranging with above-mentioned closely spaced array distributes more intensively.
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, for 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, therefore 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 there is no titania nanotube 22b completely, for each titanium dioxide unit structure, effective contact area according to the 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, increases by 2 * π * Ri * L+2 * π * Ro * L.
Hence one can see that, and the effective contact area Shi Yu unit of the nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent on average takies surface area A0 and pipe range L is closely bound up.When unit on average takies the less or pipe range L of surface area A0 when longer, effective contact area of the nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent is larger.
Via composition element depth profiles, figure is known, and in an embodiment of the present invention, when operating voltage is 10V, the pipe range of titania nanotube is about 2.52 microns (μ m); When operating voltage is 15V, the pipe range of titania nanotube is about 5.4 μ m; When operating voltage is 10V, the pipe range of titania nanotube is about 6.12 μ m.Yet, consult Fig. 5 G known simultaneously, although when applied operating voltage is promoted to 20V, the pipe range of titania nanotube can reach approximately 6.12 μ m, but because titania nanotube collapses, phenomenon is lasting to be occurred, the titania nanotube distortion aggravation of part, and the mouth of pipe of titania nanotube starts to merge, and on the mouth of pipe of titania nanotube, start to occur a large amount of unfavorable factors such as sediment, will reduce effective contact area of the nano-tube shaped solar battery thin film 2b of array and light-sensitive coloring agent.By above factor, comprehensively judged, in preferred embodiment of the present invention, preferably operating voltage should be 15V.
Dense arrangement about titania nanotube, owing to cannot directly obtaining the laboratory sample of known ' No. 538 Patent Case, therefore can only be for known the disclosed experimental result of Fig. 5 A of ' No. 538 patent specification, 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 from known, in the area of positive plate surface 500nm * 500nm, conformal into about 36 titania nanotubes, therefore can learn that known, in No. 538 Patent Case of ', unit on average takies surface area and is about 7000 square nanometers.Yet from 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, conformal into about 43 to 45 titania nanotubes, therefore can learn 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.
From above narration, due to for each titanium dioxide unit structure, unit of the present invention on average takies surface area A0 and approximately only has 5600 square nanometers to 5800 square nanometers, approximately only has ' No. 538 revealer's of Patent Case institute 80% known, in the nano-tube shaped solar battery thin film 2b of the obvious array utilizing made of the present invention, the dense arrangement 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 of titanium more regular (more consistent), when it forms titania nanotube via anode processing, the titania nanotube generating can have longer pipe range.Because disclosed titanium sprayed coating in ' No. 538 patent specification known is to be shaped with spraying method, its surperficial crystal boundary arrangement is pointed to quite chaotic and irregular, therefore the sensing of the titania nanotube generating is also quite irregular, cause the pipe range of its titania nanotube shorter; Yet, in the present invention, because being utilizes with directing silicon substrate 1, and utilize sputtering way to form titanizing metal level 2, therefore, sequentially after above-mentioned vacuum heat operation, annealing heat treatment operation and anode processing operation, in the nano-tube shaped solar battery thin film 2b of array generating, 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 longer pipe range L.
From narrating above, ' No. 538 patent compared to known, due in utilizing the nano-tube shaped solar battery thin film 2b of the produced array of the disclosed technology of the present invention, for each titanium dioxide unit structure, it is less that unit on average takies surface area A0, and the pipe range of titania nanotube 22b is longer; Apparently, utilize effective contact area of the 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 large.
Finally, please continue to refer to Fig. 8, it shows the simple making method flow chart of the nano-tube shaped solar battery thin film of the disclosed array of preferred embodiment of the present invention.As shown in Figure 8, when making the nano-tube shaped solar battery thin film 2b of array, must first prepare same directing silicon substrate 1(step 110); And go out titanizing metal level 2 at the surperficial sputter of same directing silicon substrate 1, so as to making same directing silicon substrate 1 and titanizing metal level 2 form titanizing silicon substrate 100(step 120).Then, titanizing silicon substrate 100 must be positioned over and in vacuum heat environment, carry out vacuum heat operation, so as to eliminating titanizing metal level 2 and with the residual stress (step 130) of 1 of directing silicon substrate, and titanizing silicon substrate 100 is positioned over to the annealing heat treatment operation of annealing in heat treatment environment, so as to titanizing metal level 2 is transformed into, be situated between in phase titanium coating 2a(step 140).
And then, can utilize the clean also polishing titanizing metal level 2(step 150 of electrobrightening operation), can utilize the operation of electrochemistry direct current polarization curved scanning, evaluate the optimization operational voltage value (step 160) to Jie's required operating voltage applying when phase titanium coating 2a carries out anode processing operation, simultaneously, more can utilize the operation of electrochemistry direct current polarization curved scanning, evaluate the optimization electrolyte pH-value (step 170) to Jie's electrolyte of required immersion when phase titanium coating 2a carries out anode processing operation.
Then, according to optimization operational voltage value, apply operating voltage, according to optimization electrolyte pH-value allotment electrolyte, so as to carrying out anode processing operation to being situated between at phase titanium coating 2a, making to be situated between is transformed into the nano-tube shaped solar battery thin film 2b of array at phase titanium coating 2a, and the surface of the nano-tube shaped solar battery thin film 2b of array has a plurality of titania nanotube 22b(steps 180 of arranging with closely spaced array).Finally, apply revers voltage, make the nano-tube shaped solar battery thin film 2b of array from departing from (step 190) with directing silicon substrate 1, for making DSSC (Dye-Sensitized Solar Cell; The use of positive plate DSSC).
Such as those skilled in the art, no matter be via experimental results show that or qualitative analysis, all be appreciated that, in the present invention, because being has the same directing silicon substrate 1 of single arrangement directive property as base material, and utilize the mode of sputter to make the hungry titanizing metal level 2 in surface that is coated on same directing silicon substrate there is the 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 longer 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 there is larger surface area.Therefore, when utilizing the nano-tube shaped solar battery thin film 2b of the produced array of the present invention to make the positive plate of solar cell, can make to there is larger contact area between the titanium dioxide on the nano-tube shaped solar battery thin film 2b of array surface and light-sensitive coloring agent, so as to promoting the photoelectric conversion efficiency of solar cell, and then obtain more efficiently the electric energy that can supply human use.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art are when making according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the appended claim of the present invention.
Claims (11)
1. a manufacture method for the nano-tube shaped solar battery thin film of array, is characterized in that, comprises following steps:
(a) prepare together directing silicon substrate;
(b) at this, the surperficial sputter with directing silicon substrate goes out a titanizing metal level to form a titanizing silicon substrate;
(c) this titanizing silicon substrate is positioned over and in a vacuum heat environment, carries out a vacuum heat operation, so as to eliminating this titanizing metal level and this is with the residual stress between directing silicon substrate;
(d) this titanizing silicon substrate is positioned over and in an annealing heat treatment environment, carries out an annealing heat treatment operation, so as to making this titanizing metal level be transformed into Jie at phase titanium coating, wherein, this Jie is mainly comprised of the sharp ore deposit of titanium dioxide type crystalline texture at phase titanium coating;
(e) this Jie is carried out to an anode processing operation at phase titanium coating, so as to making this Jie be transformed into the nano-tube shaped solar battery thin film of this array at phase titanium coating, and the surface of the nano-tube shaped solar battery thin film of this array has a plurality of titania nanotubes of arranging with a closely spaced array; And
(f) apply a revers voltage, the nano-tube shaped solar battery thin film of this array is departed from directing silicon substrate from this.
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 directing silicon wafer together with directing 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 is mainly comprised of the sharp ore deposit of titanium dioxide type crystalline texture at 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 maintains 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 front step (e0) that more comprises of this step (e), it is clean and this titanizing metal level of polishing.
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 complete.
9. the manufacture method of the nano-tube shaped solar battery thin film of array as claimed in claim 1, it is characterized in that, in this step (e), be that this Jie is immersed in an electrolyte at phase titanium coating, and apply an operating voltage, so as to carrying out this anode processing 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, evaluates an optimization operational voltage value of this operating voltage and an optimization electrolyte pH-value of this electrolyte.
The manufacture method of the nano-tube shaped solar battery thin film of 11. array as claimed in claim 10, it is characterized in that, in this step (e1), when the area of this titanizing silicon substrate is 2cm * 2cm, this optimization operational voltage value is 10V to 20V, and the hydrofluoric acid that comprises 1.2vol.% in the modulation of this electrolyte formula and the sulfuric acid of 10vol.%.
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| CN1740406A (en) * | 2004-08-28 | 2006-03-01 | 清华大学 | Nanometer silicon wire structure and its growth process |
| 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 |
| 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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| JP4669352B2 (en) * | 2005-09-05 | 2011-04-13 | 国立大学法人京都大学 | Method for producing titania nanorod and dye-sensitized solar cell using the titania nanorod |
| KR101043584B1 (en) * | 2008-08-20 | 2011-06-22 | 한국과학기술원 | TiO2-xNx nanotubes by selective doping of atomic nitrogen states and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1740406A (en) * | 2004-08-28 | 2006-03-01 | 清华大学 | Nanometer silicon wire structure and its growth process |
| 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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| JP特开2007-70136A 2007.03.22 |
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