CN102082184A - Solar cell and method for manufacturing the same - Google Patents

Solar cell and method for manufacturing the same Download PDF

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Publication number
CN102082184A
CN102082184A CN2010102624020A CN201010262402A CN102082184A CN 102082184 A CN102082184 A CN 102082184A CN 2010102624020 A CN2010102624020 A CN 2010102624020A CN 201010262402 A CN201010262402 A CN 201010262402A CN 102082184 A CN102082184 A CN 102082184A
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layer
solar cell
matrix
quantum dot
sublayer
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CN102082184B (en
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许闰成
朴胜一
金根柱
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DMS Co Ltd
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SNT Co Ltd
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Priority claimed from KR1020090117817A external-priority patent/KR101075149B1/en
Priority claimed from KR1020090125015A external-priority patent/KR101093005B1/en
Priority claimed from KR1020090125008A external-priority patent/KR20110068161A/en
Priority claimed from KR1020090125001A external-priority patent/KR101079213B1/en
Priority claimed from KR1020090124969A external-priority patent/KR101124490B1/en
Application filed by SNT Co Ltd filed Critical SNT Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a solar cell and a method for manufacturing the same.The solar cell comprises a matrix and the surface of the matrix is processed to reduce solar reflection coefficient.A c formed by vapour deposition is arranged on the surface of the matrix as a film substance.An N junction layer is formed on the quantum dot layer and an emitter is formed on the N junction layer.A plurality of charges isolated from the incident light transferred to the quantum dot layer are transferred to the emitter.An anti-reflection coating layer is formed on the upper portion of the N junction layer and the emitter to prevent the reflected light.Band gap energy from different regions can be generated when light passes through the N junction layer and the quantum dot layer.Therefore, the charges separated by the band gap energy of different regions generate electric power.The wavelength of the light widely incorporated into the solar spectrum can increase the generated electric power, thereby manufacturing solar cells of ultra-high efficiency.

Description

Solar cell and manufacture method thereof
Technical field
The invention relates to a kind of solar cell and manufacture method thereof, particularly relevant for a kind of use widely solar spectrum to produce the solar cell and the manufacture method thereof of electric power.
Background technology
Solar cell is a kind of semiconductor device that transform light energy is become electric energy.When the light corresponding with the band gap energy of solar cell material is absorbed into battery, promptly produce electric charge, and solar cell separates and collect these electric charges.
General conventional solar cell connects the face crystallization by a single PN and forms.This solar cell can not use all frequency spectrums to produce electric charge, because this solar cell only comprises a kind of band gap energy, can only use the wavelength in near-infrared wavelength zone in Long wavelength region and visible light.
Therefore, have at present during a large amount of solar cell developmental researches just carrying out, these researchs are in conjunction with the material of different band gap energy, extensively obtaining electric charge from each wavelength, but not only use the single face solar cell that connects.
Summary of the invention
Because the problem that above-mentioned known technology exists, purpose of the present invention be exactly provide a kind of use widely solar spectrum to produce the solar cell and the manufacture method thereof of electric power.
According to purpose of the present invention, a kind of solar cell is proposed, it comprises a matrix, and this stromal surface is handled to reduce sun reflection coefficient.One quantum dot layer is by vapour deposition, and forms film substrate in stromal surface.One N connects surface layer and is formed on quantum dot layer top.One emitter-base bandgap grading is formed at N and connects surface layer, and is sent to this emitter-base bandgap grading by transmission to a plurality of electric charges that the incident light of this quantum dot layer separates.One prevents to reflect cover layer is formed at top and the emitter-base bandgap grading that N connects surface layer, to prevent reverberation.
Wherein, quantum dot layer is formed at a sandwich construction that is stacked by quantum dot layer, and this sandwich construction has different band gap energy.
Wherein, quantum dot layer is produced by initial enlargement one film substrate, and this film substrate have one be different from matrix to the atom island atom size of (atom island).
Wherein, each layer thickness of quantum dot layer is 1 to 20 rice how.
Wherein, film substrate comprises silicon dioxide (SiO 2), silicon nitride (SiN x), silica (SiO), aluminium oxide (Al 2O 3), magnesium oxide (MgO), strontium titanates (SrTiO3), tantalum oxide (Ta3O5), titanium dioxide (TiO2), magnesium fluoride (MgF2), zinc oxide (ZnO), tin indium oxide (ITO), silicon (Si) form at least one.
According to purpose of the present invention, reintroduce a kind of method of making solar cell, it comprises the following step: prepare a matrix; The surface of handling this matrix is to reduce the reflection of incident light coefficient of this stromal surface; Form a quantum dot layer, this quantum dot layer is handled the surface of matrix by vapour deposition one film substrate in this; Form a N and connect surface layer in quantum dot layer; Form an emitter layer, this emitter layer connects surface layer by heat treatment N and forms; Remove a phosphosilicate glass, this phosphosilicate glass results from this N and connects surface layer when forming this emitter layer; And form one and prevent to reflect cover layer and connect surface layer and this emitter layer in this N.
Wherein, film substrate comprises silicon dioxide (SiO 2), silicon nitride (SiN x), silica (SiO), aluminium oxide (Al 2O 3), magnesium oxide (MgO), strontium titanates (SrTiO3), tantalum oxide (Ta3O5), titanium dioxide (TiO2), magnesium fluoride (MgF2), zinc oxide (ZnO), tin indium oxide (ITO), silicon (Si) form at least one.
Wherein, the step that forms this quantum dot layer is to be executed in a sandwich construction that is stacked by quantum dot layer, and this sandwich construction has different band gap energy.
Wherein, the step that forms this quantum dot layer is for being produced by initial enlargement one film substrate, and this film substrate have one be different from matrix to the atom island atom size of (atom island).
Wherein, the step that forms this quantum dot layer comprises one film substrate of vapour deposition from level to level in a stratiform structure, and the film substrate of this vapour deposition of heat treatment.
Wherein, the step that forms this quantum dot layer comprises successively one film substrate of vapour deposition repeatedly at least one layer structure, and this film substrate of one deck vapour deposition at least of heat treatment.
Wherein, the step that forms this quantum dot layer comprises: form the surface of a shade in this matrix, this shade has the hole of 0.1 to 20 micron of a diameter; See through this hole, vapour deposition one film substrate is in this matrix; And remove this this film substrate of shade after-baking.
Wherein, each layer thickness of quantum dot layer is 1 to 20 rice how.
Wherein, more comprise the following step: connect in the surface layer or produce a selectivity emitter layer afterwards forming this N.
According to purpose of the present invention, other proposes a kind of solar cell, and it comprises a matrix, and this stromal surface is handled to reduce sun reflection coefficient.One N connects surface layer and is formed on this matrix.One electricity slurry sublayer is made up of a plurality of metallics and is formed at the top that this N connects surface layer.One prevents to reflect the top that cover layer is formed at this electricity slurry sublayer, to prevent reverberation.
Wherein, the processing of stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, those metallics of electricity slurry sublayer intersperse among N and connect the whole surface of face.
Wherein, electricity slurry sublayer comprises those metallics, and those metallics have a how penetration region (tunneling region) of rice of diameter 1 to 30.
Wherein, electricity slurry sublayer comprises those metallics, and those metallics have a how optical diffraction district of rice of diameter 30 to 100.
Wherein, those metallics of electricity slurry sublayer comprise the sieve aperture kenel that is formed by a plurality of holes.
Wherein, electricity slurry sublayer comprises a metal particle layer in a sieve aperture kenel, and this sieve aperture kenel is coated the most nearly 30 those metallics of rice how of thickness.
Wherein, those metallics comprise gold (Au), silver (Ag), copper (Cu), tweezer (Ni), chromium (Cr), iron (Fe), tungsten (W), molybdenum (Mo), wherein at least one item of zinc (Zn).
According to purpose of the present invention, other proposes a kind of method of making solar cell, and it comprises the following step: prepare a matrix; The surface of handling this matrix is to reduce the reflection of incident light coefficient of this stromal surface; Remove a phosphosilicate glass; Form an electricity slurry sublayer, this electricity slurry sublayer is made up of a plurality of metallics and is formed at the top that this N connects surface layer; And form one and prevent to reflect cover layer.
Wherein, the step of handling this stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, form the step of this electricity slurry sublayer for disperseing those metallics to form a metal particle layer.
Wherein, the even dispersion diameter of step that forms this electricity slurry sublayer is 1 to 30 those metallics of rice how.
Wherein, form the step of this electricity slurry sublayer for forming a metal particle layer in a sieve aperture kenel that forms by a plurality of holes.
Wherein, the step that forms this electricity slurry sublayer is for forming a metal particle layer in a sieve aperture kenel, and this sieve aperture kenel is coated the most nearly 30 those metallics of rice how of thickness.
Wherein, those clipped wire subsystems comprise gold (Au), silver (Ag), copper (Cu), tweezer (Ni), chromium (Cr), iron (Fe), tungsten (W), molybdenum (Mo), wherein at least one item of zinc (Zn).
Wherein, the scanning sputter gun is used to disperse those metallics to starch the sublayer to form this electricity, and a particle density of each injection unit are is 10 13To 10 17Individual atom.
According to purpose of the present invention, a kind of solar cell is proposed again, it comprises a matrix, and this stromal surface is handled to reduce sun reflection coefficient.One layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by this matrix of etching.One N connects surface layer, is formed at the top of this matrix.One prevents to reflect cover layer, is formed at the top that this N connects face, to prevent reverberation.
Wherein, the processing of stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, layer of photonic crystals comprises a plurality of needle-like etched trench, and these a plurality of needle-like etched trench are formed by the etching of superficial makings layer.
Wherein, the diameter of needle-like etched trench is 30 to 200 rice how, and comprises several irregular needle-likes that form in the periodic lattice structure partly, and those irregular needle-likes partly sizes are 0.1 to 2 micron.
Wherein, the superficial makings layer has the irregular part of several tapers, and the irregular part of those tapers has 4 to 10 microns interval.
According to purpose of the present invention, a kind of method of making solar cell is proposed again, it comprises the following step: prepare a matrix; The surface of handling this matrix is to reduce the reflection of incident light coefficient of this stromal surface; Form a layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by this matrix of etching; Form a N and connect surface layer on this matrix, and this layer of photonic crystals is formed at this matrix; Remove a phosphosilicate glass; And form one and prevent to reflect cover layer.
Wherein, the step of handling this stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, the step that forms this layer of photonic crystals comprises to be etched with and forms a plurality of needle-like etched trench.
Wherein, etched step is for using reactive ion-etching and induction coupling electricity slurry method.
Wherein, the step that forms this layer of photonic crystals comprises: coat a constrictive type photoresistance and a sclerosis; Form a shade type sample, this shade type sample has a plurality of type sample holes, and those type sample holes are corresponding with photonic crystal stratotype sample on the constrictive type photoresistance; By those type sample holes to expose this matrix of this matrix and etching; Remove this shade type sample; And by the diffusion phosphorus connect surface layer in the matrix that this shade type sample removes to form a N.
Wherein, the step that forms this shade type sample comprises utilizes a stamp module to form those type sample holes in this matrix, and this stamp module has the irregular part of corresponding this photonic crystal stratotype sample.
Wherein, the size of shade type sample is 0.1 to 2 micron.
Wherein, the step of this matrix of etching is radiation one ion beam.
Wherein, etched step is for using reactive ion-etching and induction coupling electricity slurry method.
According to purpose of the present invention, other proposes a kind of solar cell, and it comprises a matrix, and this stromal surface is handled to reduce sun reflection coefficient.One layer of photonic crystals is the surface that is formed at this matrix, and this layer of photonic crystals is made up of a plurality of trickle metallics and a plurality of quantum wire, and those quantum wires are formed at those trickle metallics bottoms with the incident light of reflection from inside.One N connects surface layer, is formed on this layer of photonic crystals.One prevents to reflect cover layer, is formed at the top that this N connects surface layer, to prevent reverberation.
Wherein, the processing of stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, those quantum wires of layer of photonic crystals are a needle-like kenel, and those quantum wires are formed in those metallic bottoms by vapor deposited silicon.
Wherein, the diameter of those metallics is 5 to 50 rice how.
Wherein, the length of those quantum wires is 10 to 100 rice how.
According to purpose of the present invention, other proposes a kind of method of making solar cell, and it comprises the following step: prepare a matrix; The surface of handling this matrix is to reduce the reflection of incident light coefficient of this stromal surface; Form the surface of a layer of photonic crystals in this matrix, and this layer of photonic crystals is made up of a plurality of trickle metallics and a plurality of quantum wire, those quantum wires are formed at those trickle metallics bottoms with the incident light of reflection from inside; Form a N and connect surface layer on this matrix, and this layer of photonic crystals is formed at this matrix; Remove a phosphosilicate glass; And form one and prevent to reflect cover layer.
Wherein, the processing of stromal surface comprises and knits reason to form a superficial makings layer in this stromal surface.
Wherein, the step that forms this layer of photonic crystals comprises: by spray a plurality of metallics in the surface of this matrix to form those trickle metallics; And vapor deposited silicon is in the bottom of those trickle metallics and produce those quantum wires.
Wherein, form trickle metallic step for the scanning sputter gun disperseing those metallics, and those metallic density of per unit area are 10 13To 10 17Individual atom.
According to purpose of the present invention, other proposes a kind of solar cell, and it comprises a matrix, and this stromal surface is handled to reduce sun reflection coefficient.One layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by this matrix of etching.One quantum dot layer by vapour deposition, and forms a film substrate on this layer of photonic crystals top.One N connects surface layer, is formed on this quantum dot layer top.One prevents to reflect cover layer, is to be formed at the top that this N connects surface layer, to prevent reverberation.
Wherein, solar cell more comprises a selectivity emitter layer and connects on the surface layer in this N.
Wherein, solar cell more comprises an electricity slurry sublayer, and this electricity slurry sublayer is positioned at this N and connects surface layer top and be made up of a plurality of metallics.
According to purpose of the present invention, other proposes a kind of method of making solar cell, and it comprises the following step: prepare a matrix; The surface of handling this matrix is to reduce the reflection of incident light coefficient of this stromal surface; Form a layer of photonic crystals, and the lattice structure of this layer of photonic crystals tool one-period property arrangement, this lattice structure is formed by this matrix of etching; Form a quantum dot layer,, and form a film substrate on this layer of photonic crystals top by vapour deposition; Form a N and connect surface layer on this matrix, and this quantum dot layer is formed at this matrix; Remove a phosphosilicate glass, this phosphosilicate glass is formed at this N and connects on the surface layer; Form an emitter layer, this emitter layer connects surface layer by this N of heat treatment and gets; And form one and prevent to reflect cover layer on this emitter layer.
So, connect the quantum dot that surface layer and multilayer form when light passes in N, may generate the band gap energy from zones of different, therefore, each regional band gap energy makes separation of charge, and the charge generation electric power of these separation.So the wavelength of including solar spectrum widely in can increase the electric power of generation, and can make the solar cell of EHP.
To narrate in following execution mode towards reaching advantage about of the present invention other, above-mentioned information obviously is presented in the execution mode in a way, or via putting into practice this invention more understandings is arranged.
Description of drawings
Fig. 1 is the sectional view according to the solar cell embodiment of this invention;
Fig. 2 is the flow chart of solar cell method one embodiment of the present invention;
Fig. 3 is the processing procedure figure of solar cell method one embodiment of the present invention;
Fig. 4 is the sectional view of solar cell method one embodiment of the present invention;
Fig. 5 is the sectional view with reference to the solar cell method embodiment of another invention;
Fig. 6 is the electricity slurry sublayer explanation of another embodiment of the present invention;
Fig. 7 is in the solar cell of the present invention, is formed the plane graph of electricity slurry sublayer embodiment by spray method;
Fig. 8 is the flow chart of another embodiment of method for manufacturing solar battery of the present invention;
Fig. 9 is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention;
Figure 10 is the sectional view of another embodiment of solar cell method of the present invention;
Figure 11 is the flow chart of method for manufacturing solar battery one embodiment of the present invention;
Figure 12 is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention;
Figure 13 is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention;
Figure 14 is the sectional view of another embodiment of solar cell method of the present invention;
Figure 15 is the flow chart of another embodiment of method for manufacturing solar battery of the present invention;
Figure 16 is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention;
Figure 17 is the sectional view of another embodiment of solar cell method of the present invention;
Figure 18 is the flow chart of another embodiment of method for manufacturing solar battery of the present invention; And
Figure 19 is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention.
Among the figure:
10,110: matrix
12: the superficial makings layer
14: quantum dot layer
14a: trickle metallic
14b: quantum wire
16,54,94:N connects surface layer
16a: metal nanoparticle
16b: metal particle layer
16c: hole
17: the selectivity emitter layer
18: prevent to reflect cover layer
19,24: groove
20,22,26,28: electrode
20,22,26,28: electrode
21: the selectivity emitter layer
30: the splash rifle
56,96,170,190: electricity slurry sublayer
104: layer of photonic crystals
113: the constrictive type photoresistance
113a: type sample hole
116: rice impression mould how
116a: irregular component
S11-S20: step
Embodiment
Though the present invention with reference to being stated as certain embodiments, manyly be proficient in the technical staff and understanded, and claim that is defined as adding and phase jljl thereof in the change and the modification that do not depart from the present invention and made.Run through in the narration of the present invention, avoid some when point of the present invention when some science and technology of narration is decided to be, suitable execution mode will be omitted.
When similarly being " first " with " second " when these vocabulary were used to narrate many different compositions, this composition never was restricted to above vocabulary, above vocabulary is only used as the different composition of identification.
The vocabulary of this narration is only for being used to narrate some embodiment, and must only be limited to the present invention, unless clearly be used for other aspects, be expressed as odd number and comprised many meanings.In present narration, for example " constitute " or " by ... form " expression be in order to specify a feature, a number, a step, an operation, an element, a part or its composition, and can not be configured and get rid of any one or more other the existence or possibility of feature, number, step, operation, element, part or its composition.
Invent solar cell and the manufacture thereof of some embodiment according to this, will be in the below more detailed and with reference to diagram narrated, no matter these composition figure numbers all have been provided identical reference number or consistent, and omitted unnecessary explanation.
See also Fig. 1, it is the sectional view according to the solar cell embodiment of this invention.Among the figure, this solar cell of inventing an embodiment has the electrode that is formed by chip type on matrix 10, and superficial makings layer 12 is arranged with minimization matrix 10 lip-deep solar energy reflections.
Furthermore, quantum dot layer 14 is the upper sections that are formed at superficial makings layer 12, and is formed in bedded structure on the matrix 10.Quantum dot layer 14 is formed at least one bedded structure according to an embodiment of this invention.For example, quantum dot layer 14 is formed at the structure of a multilayer, and every layer thickness is 1 to 20 rice how.And better situation is the structure that quantum dot layer 14 is formed at the First Five-Year Plan layer, and total thickness is 5 to 100 rice how.
N connects the top that surface layer 16 is formed at quantum dot layer 14, and N connects surface layer 16 via many diverse ways, in the diffusion of quantum dot layer 14 upper section phosphorus and form.At this, because matrix 10 is the P type, single P-N connects face and forms along the part that connects face because N connects the cause of surface layer 16, should be right along the electronics-electric hole of subsidiary light generation ionization that connects face portion and separation.Part connects the light bump quantum dot layer 14 of surface layer 16 and has further discharged electric charge by N.When quantum dot layer 14 formed in multi-ply construction, every layer was only reacted the wavelength with specific band gap energy and discharges electric charge.
Prevent to reflect cover layer (ARC) 18 and be formed at the upper portion that N connects surface layer 16 and assign to prevent reflection of light, so the two-sided of matrix 10 all two-sidedly is all outage by what laser treatment N connect surface layer 16.Electrode is set at the top and the below part of matrix 10, so they can make external electric connect.
See also Fig. 2, it is the flow chart of solar cell method one embodiment of the present invention, and Fig. 3 is the processing procedure figure of solar cell method one embodiment of the present invention.As shown in Figures 2 and 3, a kind of manufacture method of solar cell embodiment of the present invention comprises the wafer matrix 10 of preparing to comprise silicon (S11).The surface of wafer matrix 10 is followed and is processedly reflected with the light on the minimum wafer matrix (S 12).For reaching this purpose, the surface of wafer matrix 10 is at first processed to eliminate damage, for example eliminates jagged damage.The purpose of this processing is broken or any wafer matrix 10 lip-deep foreign bodys for eliminating the fragment that produces when wafer matrix 10 is cut.
So superficial makings layer 12 is by organizing wafer matrix 10 to be formed, it is to increase the absorption of light for the loss that reduces surface reflection reaches by storing light that superficial makings layer 12 forms, and can reflect incident light (S12) via formation pyramid or dihedral vertebra type, porous or irregular type on the surface of matrix 10.
Quantum dot is formed on the matrix 10 the superficial makings layer 12 that forms via organizational process, is formed at the textural of one deck at least at this quantum dot 14.
See also Fig. 4, it is the sectional view of solar cell method one embodiment of the present invention, illustrated among the figure that (a) multi-layer quantum point layer 14 reaches the individual layer quantum dot layer 14 that (b) is formed at stromal surface on the solar cell, quantum dot layer 14 can form sandwich construction or the single layer structure shown in Fig. 4 (b) shown in Fig. 4 (a).
According to the multi-layer quantum point layer 14 of one embodiment of the invention is that constitutive property according to matrix 10 forms, and forms film substrate, and this kind multi-layer quantum point layer 14 forms by stacking the quantum dot layer with different band gap energy.This kind multi-layer quantum point layer 14 also can by from matrix 10 to the atom island, generate and to have not that the film substrate of homoatomic size forms.
For quantum dot layer 14 is formed multi-ply construction, the individual layer quantum dot layer by stacking in layer, and has repeated the step of heat treatment vapor deposition film material via vapour deposition.Quantum dot layer 14 is via repeating the vapor deposition film material in the structure of one deck at least, and heat treatment vapor deposition film material layer and forming simultaneously, but the formation of quantum dot layer 14 is not limited thereto.
Quantum dot layer 14 can be by utilizing the island growth pattern to do vapour deposition, and gas-phase depositing materials comprises carborundum (SiC) for example, silicon dioxide (SiO2), zinc oxide (ZnO), the material of rice silicon metal (nano-crystalline Si-H) class how.In island was grown up, the reciprocation between film substrate had accounted for main status.
According to this embodiment, quantum dot layer 14 becomes long pattern to form by growth pattern in layer in the multi-ply construction or island, and how rice constitutes each layer of quantum dot layer 14 by the semiconductor with the quantum dot size that is about De Buluoyi (de Broglie) wavelength.
Invent the solar cell of an embodiment according to this, the electric charge through reacting separated charge and collection to separate owing to incident light on the quantum dot layer 14 and the quantum dot of each layer, and then produce electric energy.
The relation of quantum dot size and quantum dot layer 14 each layer band gap energy shown in equation 1, square being inversely proportional to of band gap energy and lateral size of dots.
Eg = 2 π 2 ζ 2 μ D 2 + E 0 ... ... ... ... .. side
Formula 1
At this Eo is the optical energy band crack energy of body silicon, and D is the diameter of crystal.
According to equation 1, the how rice silicon metal quantum dot average diameter with band gap energy 2.6eV is
Figure BDA0000024986340000152
Because the size of quantum dot is relevant with the band gap energy, and is called as quantum size effect, when quantum dot forms in multi-ply construction, has allowed light to be absorbed at many different wavelength.
According to this embodiment, quantum dot is present in the quantum excitation layer and this quantum excitation layer can stack in below five layers, and the thickness of each quantum excitation layer is about 1 to 20 rice how, and the gross thickness of five layers of quantum dot layer is about how rice (S13) of 5-100.
N connects surface layer 16 and is formed at quantum dot layer 14 and forms after the multi-ply construction, and N connects surface layer 16 and comprises hydrogen phosphide (PH via use 3) silane (SiH 4) and chemical vapor deposition unit form N type silicon layer, N connects surface layer 16 can form single or multiple lift.When N connect surface layer 16 formation individual layers, the phosphorus of per unit volume was controlled in 10 16-21In the scope of individual atom.On the other hand, when N connect surface layer 16 and forms multilayers, one deck need increase the content of phosphorus when forming to the top from the bottom.
N connects surface layer 16 fillings and for example comprises when phosphorus mixes and can become emitting layer, connect surface layer 16 at this N and be formed sandwich construction, and each layer of structure have the phosphorus of varying number, for example when structure from the bottom during to the top, quantity is 10 16To 10 18, and to 10 20Cubic centimeter/one, after N connect surface layer 16 formation, a selectivity emitter layer 17 can further form to improve the ability (S15) of collection electronics, according to this embodiment, the selectivity emitter layer forms via laser beam local injection energy, and can or form the back generation when N connects surface layer 16 formation.
In detail, phosphorus pentoxide (P 2O 5) layer (pre-vapour deposition) is by high temperature phosphorus oxychloride (POCl 3) and oxygen (O 2) reaction, and phosphorus pentoxide (P 2O 5) phosphorus (P) of layer does heat treatment to transmit and to be diffused into silicon (Si) and to form emitting layer when high temperature.Emitting layer can produce electrical potential energy to simplify the transmission of separated charge to the N layer.According to this embodiment, selectivity emitter layer 17 at emitting layer, or adopts that each diffusion process partly forms on heating and the laser radiation matrix 10 by local laser radiation.
Before using laser to form selectivity emitter layer 17, can form the formation that the P material layer of high concentration comes accelerated selection emitter layer 17 with mode of printing by use part at laser.Atom can spread from the high concentration to the low concentration when solid-state, up to atom under the heating situation never uniform concentration become uniform concentration.
Diffusion phenomena can be by equation 2 expression, and according to first Fick (Fick ' s) diffusion law, diffusion comes across the gradient of responding concentration.
J = - D ∂ C ∂ x ... ... ... ... the .. equation
Formula 2
Furthermore, diffusion coefficient D improves rapidly when temperature increases, and this function is shown in equation 3:
D = D 0 e - Q dT ... ... ... ... the .. equation
Formula 3
At this Do is the constant of temperature influence not, and T is a temperature, and the Q in exponential function is excitation energy and is about 2 to 5eV according to the material difference.
For example, when Q=2eV and Do=8x10-5m2/sec, if T=300K, D is about 10-38m2/sec, if when T=1500K, D rapidly increases to about 10-11m2/sec.
When matrix 10 when carrying out diffusion process, (phosphorussilicate glass PSG) can be removed phosphosilicate glass, and phosphosilicate glass has comprised phosphorus oxychloride (POCl 3) and the phosphorus that between diffusion process, reacts of oxygen, and comprise impurity among the silicon, so connecing at N, phosphosilicate glass should be removed (S16) after surface layer 16 forms.
Prevent to reflect cover layer 18 type when the N layer forms and be formed on the matrix 10, the formation that prevents to reflect cover layer 18 is chemical vapour deposition (CVD) instrument or the splash instrument (S17) that strengthens by the electricity slurry, reaches the vapour deposition of silicon nitride (SiNx).
Because matrix 10 is connected with the surface of all N layers, matrix 10 can be at two-sided generation groove cutting off electricity, and the bottom that electrode is formed at matrix 10 and head portion are with being connected as external electric.
See also Fig. 5, it is the sectional view with reference to the solar cell method embodiment of another invention.The solar cell of invention has comprised the matrix of being prepared by the wafer form 10 as shown in Figure 5, and superficial makings layer 12 is formed at the surface of matrix 10 to minimize the reflection of solar energy.Consist of P type crystal and the N of matrix connect surface layer 54 diffuseing to form for phosphorus.
Electricity slurry sublayer 56 is formed at the surface that P-N connects face, according to embodiment, electricity slurry sublayer 56 forms by spraying Nai Miyin (Ag) particle, also can be by spraying gold (Au), silver (Ag), copper (Cu), nickel (Ni), chromium (Cr), iron (Fe), tungsten (W), molybdenum (Mo), the mixture of zinc (Zn) or its nanoparticle forms electricity slurry sublayer 56, but not only is limited to this.
Electricity slurry sublayer 56 has little electromagnetic interference phenomenon when light incident, the light incident in the metal surface can produce ripple via interference phenomenon, and incident light thus electromagnetic wave vibrations particle with efficient scattered light.At this, when incident light had specific resonance color, scattered light can also generation part of phase mutual interference overlap phenomenon so that better dispersion effect to be provided.
Preventing to reflect cover layer 18 forms to prevent the reflection of solar energy at electricity slurry sublayer 56 upper sections.Groove 19 then is formed on the two-sided to disconnect electricity of matrix 10, and electrode 20,22 is formed at the below and the upper section of matrix 10 afterwards.
See also Fig. 6, it is the electricity slurry sublayer explanation of another embodiment of the present invention.Represented among Fig. 6 (a) that electric slurry sublayer 56 can be formed by even sprinkling metal nanoparticle 16a, according to this embodiment, metal nanoparticle 16a is about 1 to 30 rice how at the diameter of wearing the tunnel zone, and according to this embodiment, the diameter of metal nanoparticle 16a in the optical diffraction zone is about 30 to 100 rice how.
See also Fig. 7, it is in the solar cell of the present invention, is formed the plane graph of electricity slurry sublayer embodiment by spray method.Spray method comprise splash rifle 30 with sputtered metal particle and module (not shown) with mobile solar energy matrix 10 or splash rifle 30.
30 splashes of splash rifle the metallic of fixed qty on matrix, can be changed by the distance of 10 of the translational speed of the shape of splash rifle 30, splash rifle 30, splash rifle 30 and matrix, the electric current that splash rifle 30 uses, the pressure of processing gas etc. by the metallic quantity of splash on stromal surface.According to this embodiment, when the metallic that forms electricity slurry sublayer during by the splash of splash program, the per unit area on the matrix 10 has 10 approximately 13To 10 17Individual atom.
Among Fig. 6 (b), electricity slurry sublayer 56 forms metal particle layer 16b with web form and many hole 16c.According to this embodiment, metal particle layer 16b can have 30 how the following thickness of rice so that optical channel to be provided.When electricity slurry sublayer 56 by the sputtered metal particle after matrix 10 forms, prevent to reflect cover layer 18 formation to prevent reflection of light.
Further, groove 19 is formed at the two-sided by using laser to make N connect surface layer 54 outages of matrix 10, and bottom and summit portion that electrode 20,22 is formed at matrix 10 link with external electrical.
See also Fig. 8, it is the flow chart of another embodiment of method for manufacturing solar battery of the present invention.See also Fig. 9, it is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention.As Fig. 8 and shown in Figure 9, comprise the wafer matrix 10 of preparing to comprise silicon according to the method for manufacturing solar battery of present embodiment, matrix 10 surperficial processed to minimize stromal surface (S12) reflection of incident light.
For this target, the surface of wafer matrix 10 is at first processed to eliminate injury, and for example the sawtooth injury removes.This processing is the fragment slight crack that produces when wafer matrix 10 is cut in order to eliminate, or any impurity in wafer matrix 10 surfaces.
The superficial makings layer 12 then texture on wafer matrix 10 forms, the formation of superficial makings layer 12 to be lowering the surface reflection loss and storing light increasing the absorption of light, by forming pyramid or dihedral taper, multiple hole or form irregular shape with the reflection incident light on matrix 10 surfaces perhaps.
It is to form with N type silicon (Si) layer that N connects surface layer 94, by using chemical vapour deposition (CVD) instrument (S13) and comprising hydrogen phosphide (PH 3) silane (SiH 4), when the diffusion process on matrix 10 was performed, phosphosilicate glass (PSG) had been removed, and phosphosilicate glass is one to comprise the oxide of phosphorus, by the phosphorus oxychloride (POCl in diffusion process 3) and oxygen between reaction produce, and comprised the impurity that exists in the silicon, be removed after surface layer 94 forms (S14) so phosphosilicate glass connects at N.
After phosphosilicate glass was removed, electricity slurry sublayer 96 was formed at the upper section that N connects surface layer 94, and electricity slurry sublayer 96 is by to use splash rifle 30 to move matrix 10 or to spray the metal nanoparticle with fixing rate travel.Have 10 approximately at per unit area 13To 10 17Individual metallic is sprayed onto on the matrix 10 to form electricity slurry sublayer 96 (S15).
Electricity slurry sublayer 96 prevents to reflect cover layer 18 and forms to prevent reflection of light after forming on the matrix 10, prevents to reflect cover layer 18 and can form (S16) with electricity slurry enhanced chemical vapor deposition method or splash method by vapour deposition silicon nitride (SiNx).Since matrix 10 is connected to all surfaces by the N layer, it can be de-energized the two-sided of matrix 10 by producing groove 19.The bottom that electrode is formed at matrix 10 provides external electric to be connected (S17) with head portion.
See also Figure 10, it is the sectional view of another embodiment of solar cell method of the present invention.As shown in Figure 10, the electrode of the solar cell of this inventive embodiment on matrix 10 forms with the wafer form, and superficial makings layer 12 forms to minimize the reflection of solar energy on matrix 10 surfaces.
Layer of photonic crystals 104 has the periodic arrangement lattice structure that is formed by etched substrate 10, layer of photonic crystals 104 prevents that incident light from reflexing to the external world, and provide the lasting external world to reflect to strengthen incident light, layer of photonic crystals 104 can comprise a plurality of needle-like etched trench that formed by etched surfaces texture layer 12.
N connects surface layer 16 and is formed by the phosphorus that is diffused in needle-like etched trench top, since in this matrix 10 is the P type, because N connects the phosphorous diffusion formation of surface layer 16 with many different modes, individual layer P-N connects surface layer and forms along connecing facial part, and the electric hole that produces ionization and separation along the incident light that connects face portion is right.
Prevent to reflect cover layer 18 and be formed at head portion that N connects surface layer 16 preventing reflection of light, two-sided groove forms disconnecting electricity on the matrix, and electrode 20,22 is installed in the bottom and the head portion of matrix 10.
See also Figure 11, it is the flow chart of method for manufacturing solar battery one embodiment of the present invention.See also Figure 12, it is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention.The method for manufacturing solar battery of embodiment shown in Figure 11 and 12 comprises the wafer matrix 10 of preparing to comprise silicon (S11).Wafer matrix 10 surperficial processed to minimize the reflection of incident light in stromal surface, for this target, the surface of wafer matrix 10 is at first processed to eliminate injury, and for example the sawtooth injury removes.This processing is the fragment slight crack that produces when wafer matrix 10 is cut in order to eliminate, or any impurity on wafer matrix 10 surfaces.
Superficial makings layer 12 then forms lowering the surface reflection loss and storing light increasing the absorption of light, by forming pyramid or dihedral taper, multiple hole or form irregular shape with the reflection incident light on matrix 10 surfaces perhaps.
Layer of photonic crystals 104 is after superficial makings layer 12 forms, has the periodic arrangement lattice structure that forms by etched substrate 10, layer of photonic crystals 104 is formed on the superficial makings layer 12, and layer of photonic crystals 104 prevents that incident light from reflexing to the external world, and provides the lasting external world to reflect to strengthen incident light.
Layer of photonic crystals 104 is made up of trickle metallic 14a (as shown in figure 14) and quantum wire 14b (as shown in figure 14), and quantum wire 14b (is formed at trickle metallic 14a below part.
The formation of layer of photonic crystals 104 is to reach in the scanning splash method of shaped surface texture layer 12 on matrix 12 by spraying trickle metallic 14a, and the particle density that sprays at per unit area is about 10 13To 10 17Individual atom.The formation of layer of photonic crystals 104 is by form the needle-like etched trench with high density ion-etching etched surfaces texture layer 12.
The high density ion-etching can be by reactive ion etching (reactive ionetching, RIE) method or induction coupling electricity slurry (inductive coupled plasma, ICP) method is carried out, the program gas of high density ion-etching can be sulphur hexafluoride (S6), oxygen (O2), chlorine (Cl2), nitrogen (N2) and similar gas, and programmed pressure is 10 -2To 1 holder ear (Torr).
The needle-like etched trench is formed by the high density ion(ic) etching on superficial makings layer 12, and the needle-like etched trench has 30 to 200 how the etch pattern sample of rice and 0.1 to 2 micron lattice period.
According to this embodiment, layer of photonic crystals 104 is by forming with the high density ion-etching, and it also can form by the many additive methods that are not restricted to this.For example, layer of photonic crystals 104 can be formed by a how rice imprint method as shown in figure 13.
See also Figure 13, it is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention.Narrated the how use of rice imprint method among the figure.As shown in figure 13, wafer matrix 110 comprises ready silicon, and the superficial makings layer is formed on the wafer matrix 110 by the matrix texture, and after the superficial makings layer formed, layer of photonic crystals was then by how a rice imprint method forms.
Constrictive type photoresistance 113 is covered on the surface of matrix 110, and the sclerosis result.Constrictive type photoresistance 113 can be Light negative or electrical impedance.Type sample hole 113a by the contrast of using rice impression mould 116 how in the irregular component 116a in the type sample cycle of layer of photonic crystals, be formed on the photoresistance 113 of matrix 110, how the crystal cycle of the irregular component 116a on the rice impression mould is 0.1 to 2 rice how, and bore dia is 30 to 200 rice how.
Photoresistance 113 has the type sample hole 113a of function rice shade for how to expose the part matrix 110 with respect to photonic crystal stratotype sample.Matrix 110 is by using ion beam milling, and at this, the matrix 110 of part is by type sample hole 113a exposure and by ion beam milling.Ion(ic) etching is that (reactive ion etching, RIE) (the program gas of ion-etching can be sulphur hexafluoride (S for inductive coupled plasma, ICP) method execution for method or induction coupling electricity slurry by reactive ion etching 6), oxygen (O 2), chlorine (Cl 2), nitrogen (N 2) and similar gas, and programmed pressure is 10 -2To 1 holder ear (Torr).After etching program is finished, with photoresistance 113 usefulness of rice shade for how for example acetone be removed.
When the layer of photonic crystals with a plurality of etched trench was formed, N connect surface layer 116 and forms by spreading phosphorus from the teeth outwards, once again consult Figure 11 and 12, N connects surface layer 16 by using the chemical vapour deposition (CVD) instrument and comprising hydrogen phosphide (PH 3) silane (SiH 4), form silicon (Si) layer (S14) of N type.
When the diffusion process on matrix 10 was performed, phosphosilicate glass (PSG) had been removed, and phosphosilicate glass is one to comprise the oxide of phosphorus, by the phosphorus oxychloride (POCl in the diffusion process that connects surface layer 16 at N 3) and oxygen between reaction produce, and comprised the impurity that exists in the silicon, be removed after surface layer 16 forms (S15) so phosphosilicate glass connects at N.
Prevent to reflect cover layer 18 and can form (S16) with electricity slurry enhanced chemical vapor deposition method or splash method by vapour deposition silicon nitride (SiNx).Since matrix 10 is connected to all surfaces by the N layer, it can be de-energized the two-sided of matrix 10 by using laser to produce groove 19.The bottom that electrode 20,22 is formed at matrix 10 provides external electric to be connected (S17) with head portion.
See also Figure 14, it is the sectional view of another embodiment of solar cell method of the present invention.Among Figure 14, an embodiment of this solar cell invention comprises that electrode and superficial makings layer 12 on the wafer matrix are formed to minimize the reflection of solar energy on matrix 10 surfaces.Superficial makings layer 12 with have about 4 to 12 how the pyramidal structure at the interval of rice be formed.
Layer of photonic crystals 104 is formed on the superficial makings layer 12, and layer of photonic crystals 104 prevents that incident light from reflexing to the external world, and provides the lasting external world to reflect to strengthen incident light.Layer of photonic crystals 104 is made up of trickle metallic 14a and quantum wire 14b, and quantum wire 14b is formed at trickle metallic 14a below part.
The formation of layer of photonic crystals 104 is to reach in the scanning splash method of shaped surface texture layer 12 on matrix 10 by spraying trickle metallic 14a, and the particle density that sprays at per unit area is about 10 13To 10 17Individual atom.
According to this embodiment, spray method has as shown in Figure 7 been described the plane graph of scanning spray method, has comprised splash rifle 30 and has reached the module of not demonstration with mobile solar cell matrix 10 or splash rifle 30 to spray metallic.
30 splashes of splash rifle the metallic of fixed qty on stromal surface, can be by the metallic quantity of splash on stromal surface ... wait institute to change by the distance of 10 of the translational speed of the shape of splash rifle 30, splash rifle 30, splash rifle 30 and matrix, the electric current that splash rifle 30 uses, the pressure of processing gas, how meter the size of trickle metallic 14a is about 5 to 50.
According to this embodiment, the metal of trickle metallic can be gold (Au), silver (Ag), copper (Cu), nickel (Ni), chromium (Cr), iron (Fe), tungsten (W), molybdenum (Mo), or zinc (Zn) ... etc.
The silicon particle is spread with vapour deposition by the chemical vapour deposition (CVD) instrument, and grow in the below part of trickle metallic 14a, quantum wire 14b had low binding energy, quantum wire 14b forms to have about 10 to 100 length of rice how, when the superficial makings layer 12 of silicon particle on matrix 10 grown, trickle metallic 14a was transformed into upper section.
Trickle metallic 14a starches sub-effect vibration incident light with scattered light with electricity, and, resonance strengthened this scattered light owing to having increased scattering effect, at this, when incident light had specific resonance color, scattered light can interfere with each other and produce part and overlap existing picture so that better scattering effect to be provided.
N connects surface layer 146 and is formed by diffusion phosphorus on quantum dot layer 14, and it is made up of trickle metallic 14a and quantum wire 14b.At this, because matrix 10 is the P type, single P-N connects face and forms along the part that connects face because N connects the cause of surface layer 146, and is formed by many different modes diffusion phosphorus, and the electronics-electric hole that produces ionization and separation along the incident light that connects face portion is right.
Prevent to reflect cover layer 18 and be formed at head portion that N connects surface layer 146 preventing reflection of light, two-sided groove forms disconnecting electricity on the matrix, and electrode 20,22 is installed in the bottom and the head portion of matrix 10.
See also Figure 15, it is the flow chart of another embodiment of method for manufacturing solar battery of the present invention, see also Figure 16, it is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention, shown in Figure 15 and 16, the method for manufacturing solar battery of the embodiment of the invention comprises the wafer matrix 10 (S11) of preparing to comprise silicon.Wafer matrix 10 surperficial processed to minimize the reflection of incident light on matrix, for this target, the surface of wafer matrix 10 is at first processed to eliminate injury, and for example the sawtooth injury removes.This processing is the fragment slight crack that produces when wafer matrix 10 is cut in order to eliminate, or any impurity on wafer matrix 10 surfaces.
Superficial makings layer 12 then forms and is formed on wafer matrix 10 by texture wafer matrix 10.The formation of superficial makings layer 12 is in order to lower surface reflection loss and by storing light increasing the absorption of light, by forming pyramid or dihedral taper, multiple hole or form irregular shape with reflection incident light (S12) on matrix 10 surfaces perhaps.
After superficial makings layer 12 forms, layer of photonic crystals 14 then forms, before layer of photonic crystals 14 forms, trickle metallic 14a is sprayed on the surface of superficial makings layer 12, and trickle metallic 14a moves matrix 10 or splash rifle 30 by splash rifle 30 and sprays with fixing rate travel and form (S13).
The silicon particle is spread by the chemical vapour deposition (CVD) instrument, and grows in the below part of trickle metallic 14a to quantum wire 14b, and trickle metallic has the effect of catalyst.Therefore, further by vapour deposition and grow in the below part of trickle metallic 14a, and quantum wire 14b is had low binding energy by the silicon that spread, during quantum wire 14b growth long more, trickle metallic can be big more.
Quantum wire 14b is the most suitable to be grown to length between 10 to 100 scopes of rice how, and N connects surface layer 16 and comprises hydrogen phosphide (PH via use 3) silane (SiH 4) and chemical vapor deposition unit formation (S15).Be executed in matrix 10 at diffusion process, phosphosilicate glass (PSG) has been removed.
Phosphosilicate glass is that monoxide has comprised phosphorus oxychloride (POCl 3) and the phosphorus that between diffusion process, reacts of oxygen, and comprise impurity among the silicon, so connecing at N, phosphosilicate glass should be removed (S16) after surface layer 16 forms.Prevent to reflect cover layer 18 and be formed at the N layer that forms on the matrix 10, prevent to reflect cover layer 18 and can form (S17) with electricity slurry enhanced chemical vapor deposition method or splash method by vapour deposition silicon nitride (SiNx).
Since matrix 10 is connected to all surfaces by the N layer, it can be de-energized the two-sided of matrix 10 by using laser to produce groove 19.The bottom that electrode 20,22 is formed at matrix 10 provides external electric to be connected (S18) with head portion.
See also Figure 17, it is the sectional view of another embodiment of solar cell method of the present invention.Represented among Figure 17 that this invents the solar cell of an embodiment, the electrode and the superficial makings layer 12 that comprise on the wafer matrix 10 are formed to minimize the reflection of solar energy on matrix 10 surfaces.
Superficial makings layer 12 with have about 4 to 12 how the pyramidal structure at the interval of rice be formed.Layer of photonic crystals 14 is formed on the superficial makings layer 12, and layer of photonic crystals 14 prevents that incident light from reflexing to the external world, and provides the lasting external world to reflect to strengthen incident light.
Layer of photonic crystals 104 can comprise a plurality of needle-like etched trench that formed by etched surfaces texture layer 12, and quantum dot layer 14 forms bedded structure after the layer of photonic crystals 104 of part above the superficial makings layer 12 forms.
According to this embodiment, quantum dot layer 14 forms the structure of one deck at least, and for example, quantum dot layer 14 can be formed multi-ply construction, and every layer thickness is 1 to 20 rice how.Preferable, quantum dot layer 14 can form five layers of structure, and gross thickness is 5 to 100 scopes of rice how, and when quantum dot layer 14 formed in multi-ply construction according to one embodiment of the invention, every layer of meeting reacted the wavelength with specific relatively band gap energy and discharged electric charge.
According to this embodiment, layer of photonic crystals can further be formed at the top of quantum dot layer 14.
N connect surface layer 16 with multiple distinct methods at the upper section of quantum dot layer 14 diffusion phosphorus and form, it is made up of trickle metallic 14a and quantum wire 14b.At this, because matrix 10 is the P type, single P-N connects face and forms along the part that connects face because N connects the cause of surface layer 16, and the electronics-electric hole that produces ionization and separation along the incident light that connects face portion is right.
Part is passed N and is connect the light bump quantum dot layer 14 of surface layer 16 and discharge electric charge, electricity slurry sublayer 170 then is formed on the surface that N connects surface layer 16, according to embodiment, electricity slurry sublayer 170 forms by spraying Nai Miyin (Ag) particle, and electricity slurry sublayer 170 also can be by spraying gold (Au), silver (Ag), copper (Cu), nickel (Ni), chromium (Cr), iron (Fe), tungsten (W), molybdenum (Mo), the mixture of zinc (Zn) or its nanoparticle form electricity slurry sublayer 170, but not only are limited to this.
Electricity slurry sublayer 170 has little electromagnetic interference phenomenon when light incident, the light incident in the metal surface can produce ripple via interference phenomenon, and incident light thus electromagnetic wave vibrations particle with efficient scattered light.At this, when incident light had specific resonance color, scattered light can also generation part of phase mutual interference overlap phenomenon so that better dispersion effect to be provided.
Electricity slurry sublayer 170 is evenly sprayed the metal nanoparticle and is formed by using, and according to this embodiment, metallic is about 1 to 30 rice how at the diameter of wearing the tunnel zone, and according to this embodiment, how meter the diameter of metal nanoparticle 16a in the light scattering zone be about 30 to 100.
See also Fig. 7, it is in the solar cell of the present invention, is formed the plane graph of electricity slurry sublayer embodiment by spray method.Spray method comprise splash rifle 30 with sputtered metal particle and module (not shown) with mobile solar energy matrix 10 or splash rifle 30.
30 splashes of splash rifle the metallic of fixed qty on matrix, can be by the metallic quantity of splash on stromal surface by the distance of 10 of the translational speed of the shape of splash rifle 30, splash rifle 30, splash rifle 30 and matrix, the electric current that splash rifle 30 uses, the pressure of processing gas ... wait change.According to this embodiment, when the metallic that forms electricity slurry sublayer during by the splash of splash program, the per unit area on the matrix 10 has 10 approximately 13To 10 17Individual atom.
Electricity slurry sublayer 170 forms metal particle layer with web form and many hole.According to this embodiment, metal particle layer can have 30 how the following thickness of rice so that optical channel to be provided.Prevent to reflect cover layer 18 and be formed at the upper section of electricity slurry sublayer 20 to prevent reflection of light.
Further, groove 24 is formed at the two-sided by using laser with outage of matrix 10, and bottom and summit portion that electrode 26,28 is formed at matrix 10 link with external electrical.
See also Figure 18, it is the flow chart of another embodiment of method for manufacturing solar battery of the present invention.See also Figure 19, it is the processing procedure figure of another embodiment of method for manufacturing solar battery of the present invention.The surface of wafer matrix 10 is followed and is processedly reflected with the light on the minimum wafer matrix (S12).For reaching this purpose, the surface of wafer matrix 10 is at first processed to eliminate damage, for example eliminates jagged damage.The purpose of this processing is broken or any wafer matrix 10 lip-deep foreign bodys for eliminating the fragment that produces when wafer matrix 10 is cut.
So superficial makings layer 12 is by organizing wafer matrix 10 to be formed, it is to increase the absorption of light for the loss that reduces surface reflection reaches by storing light that superficial makings layer 12 forms, and can reflect incident light (S12) via formation pyramid or dihedral vertebra type, porous or irregular type on the surface of matrix 10.
After superficial makings layer 12 formed, layer of photonic crystals 104 then formed, and the formation of layer of photonic crystals 104 is by form the needle-like etched trench with high density ion-etching etched surfaces texture layer 12.The high density ion-etching can be carried out by reactive ion-etching or induction coupling electricity slurry method, and the program gas of high density ion-etching can be sulphur hexafluoride (S 6), oxygen (O 2), chlorine (Cl 2), nitrogen (N 2) and similar gas, and programmed pressure is 10-2 to 1 a holder ear (Torr).
The needle-like etched trench is formed by the high density ion(ic) etching on superficial makings layer 12, and the needle-like etched trench has 30 to 200 how the etch pattern sample of rice and 0.1 to 2 micron lattice period.
According to this embodiment, layer of photonic crystals 104 is by forming with the high density ion-etching, and it also can form by the many additive methods that are not restricted to this.For example, layer of photonic crystals 104 can be formed by a how rice imprint method as shown in figure 13.
Quantum dot layer 14 is formed at after layer of photonic crystals 104 on the superficial makings layer 12 forms, according to the multi-layer quantum point layer 14 of one embodiment of the invention is that constitutive property according to matrix 10 forms, and form film substrate, this kind multi-layer quantum point layer 16 forms by stacking the quantum dot layer with different band gap energy.This kind multi-layer quantum point layer 14 also can by from matrix 10 to the atom island, generate and to have not that the film substrate of homoatomic size forms.
For quantum dot layer 14 is formed multi-ply construction, the individual layer quantum dot layer by stacking in layer, and has repeated the step of heat treatment vapor deposition film material via vapour deposition.Quantum dot layer 14 is via repeating the vapor deposition film material in the structure of one deck at least, and heat treatment vapor deposition film material layer and forming simultaneously, but the formation of quantum dot layer 14 is not limited thereto.
Quantum dot layer 14 can be by utilizing island to become long pattern to do vapour deposition, and gas-phase depositing materials comprises for example carborundum (SiC), silicon dioxide (SiO 2), zinc oxide (ZnO), the material of rice silicon metal (nano-crystalline Si-H) class how.In island was grown up, the reciprocation between film substrate had accounted for main status to form quantum dot layer 16.
According to this embodiment, quantum dot layer 14 becomes long pattern to form by growth pattern in layer in the multi-ply construction or island, and how rice constitutes each layer of quantum dot layer 14 by the semiconductor with the quantum dot size that is about De Buluoyi (de Broglie) wavelength.
Layer of photonic crystals further forms on the quantum dot layer 14, and N connects surface layer 16 and then forms.N connects surface layer 16 by using chemical vapour deposition (CVD) instrument (S13) and comprising hydrogen phosphide (PH 3) silane (SiH 4), form N type silicon (Si) layer.N connects surface layer 16 can form single or multiple lift.
When N connect surface layer 16 formation individual layers, the phosphorus of per unit volume was controlled in 10 16-21In the scope of individual atom.On the other hand, when N connect surface layer 16 and forms multilayers, one deck need increase the content (S15) of phosphorus when forming to the top from the bottom.
Electricity slurry sublayer 190 is formed at the upper section that N connects surface layer 16, and electricity slurry sublayer 190 is by to use splash rifle 30 to move matrix 10 or to spray the metal nanoparticle with fixing rate travel.Have 10 approximately at per unit area 13To 10 17Individual metallic is sprayed onto on the matrix 10 to form electricity slurry sublayer 190 (S16).
Emitter layer is formed the ability (S17) of collecting electronics to improve after electricity slurry sublayer 190 forms, according to this embodiment, selectivity emitter layer 21 can the highdensity phosphorus of diffusion forms on the surface layer by connecing at N, and zonal illuminating laser beam.
Selectivity emitter layer 21 can be formed at when N connects surface layer 16 and forms or after forming, in detail, and phosphorus pentoxide (P 2O 5) layer (pre-vapour deposition) is by high temperature phosphorus oxychloride (POCl 3) and oxygen (O 2) reaction, and phosphorus pentoxide (P 2O 5) phosphorus (P) of layer does heat treatment to transmit and to be diffused into silicon (Si) and to form emitting layer when high temperature.
Emitting layer can produce electrical potential energy to simplify the transmission of separated charge to the N layer.According to this embodiment, selectivity emitter layer 21 at emitting layer, or adopts that each diffusion process partly forms on heating and the laser radiation matrix 10 by local laser radiation.
Before using laser to form selectivity emitter layer 21, can form the formation that the P material layer of high concentration comes accelerated selection emitter layer 21 with mode of printing by use part at laser.
Phosphosilicate glass (PSG) is one to comprise the oxide of phosphorus, by the phosphorus oxychloride (POCl in diffusion process 3) and oxygen between reaction produce, and comprised the impurity that exists in the silicon, should be removed (S18) so phosphosilicate glass connects at N after surface layer 16 forms (S14).
Prevent to reflect cover layer 22 and be formed at the N layer that forms on the matrix 10, prevent to reflect cover layer 22 and can form (S19) with electricity slurry enhanced chemical vapor deposition method or splash method by vapour deposition silicon nitride (SiNx).
Further, groove 24 is formed at the two-sided by using laser with outage of matrix 10, and electrode 26,28 is formed at the bottom and the summit portion (S20) of matrix 10.
Solar cell according to the embodiment of the invention comprises layer of photonic crystals 104 and quantum dot layer 14 or further comprises electricity slurry sublayer 190 or selectivity emitter layer 21.Further, the solar cell of this invention can comprise these layers 104,14,190 and 21 that all are mentioned.
That is, comprising at least one layer of photonic crystals 104, quantum dot layer 14, electricity slurry sublayer 190 or selectivity emitter layer 21 according to the solar cell of the embodiment of the invention, better situation is for comprising all 104,14,190 and 21 layers.
Though the present invention with reference to being stated as certain embodiments, manyly be proficient in the technical staff and understanded, and claim that is defined as adding and phase jljl thereof in the change and the modification that do not depart from the present invention and made.Therefore, other embodiment outside the above can be found in additional claim.

Claims (57)

1. solar cell is characterized in that: comprise:
One matrix, this stromal surface are handled to reduce sun reflection coefficient;
One quantum dot layer by vapour deposition, and forms a film substrate in described stromal surface;
One N connects surface layer, is formed on described quantum dot layer top;
One emitter-base bandgap grading is formed at described N and connects surface layer, and is sent to this emitter-base bandgap grading by transmission to a plurality of electric charges that the incident light of described quantum dot layer separates; And
One prevents to reflect cover layer, is formed at top and emitter-base bandgap grading that described N connects surface layer, to prevent reverberation.
2. solar cell as claimed in claim 1 is characterized in that: described quantum dot layer is formed at a sandwich construction that is stacked by quantum dot layer, and this sandwich construction has different band gap energy.
3. solar cell as claimed in claim 1 is characterized in that: described quantum dot layer is produced by initial enlargement one film substrate, and this film substrate has one to be different from the atom size of described matrix to the atom island.
4. as each described solar cell in the claim 1 to 3, it is characterized in that: each layer thickness of described quantum dot layer is 1 to 20 rice how.
5. as each described solar cell in the claim 1 to 3, it is characterized in that: described film substrate comprises at least one item in silicon dioxide, silicon nitride, silica, aluminium oxide, magnesium oxide, strontium titanates, tantalum oxide, titanium dioxide, magnesium fluoride, zinc oxide, tin indium oxide, the silicon composition.
6. method of making solar cell is characterized in that: comprise the following step:
Prepare a matrix;
The surface of handling described matrix is to reduce the reflection of incident light coefficient of described stromal surface;
Form a quantum dot layer, this quantum dot layer by vapour deposition one film substrate in the surface of described processing matrix;
Form a N and connect surface layer in described quantum dot layer;
Form an emitter layer, this emitter layer connects surface layer by the described N of heat treatment and forms;
Remove a phosphosilicate glass, this phosphosilicate glass results from described N and connects surface layer when forming described emitter layer; And
Formation one prevents to reflect cover layer and connects surface layer and described emitter layer in described N.
7. manufacturing solar cell method as claimed in claim 6 is characterized in that: the step that forms described quantum dot layer is executed in a sandwich construction that is stacked by quantum dot layer, and this sandwich construction has different band gap energy.
8. manufacturing solar cell method as claimed in claim 6 is characterized in that: the step that forms described quantum dot layer is produced by initial enlargement one film substrate, and this film substrate has one to be different from the atom size of described matrix to the atom island.
9. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: the step that forms described quantum dot layer comprises one film substrate of vapour deposition from level to level in a stratiform structure, and the film substrate of this vapour deposition of heat treatment.
10. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: the step that forms described quantum dot layer comprises successively one film substrate of vapour deposition repeatedly at least one layer structure, and this film substrate of one deck vapour deposition at least of heat treatment.
11. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: the step that forms described quantum dot layer comprises:
Form the surface of a shade in described matrix, this shade has the hole of 0.1 to 20 micron of a diameter;
By this hole, vapour deposition one film substrate is in described matrix; And
Remove the described film substrate of described shade after-baking.
12. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: each layer thickness of described quantum dot layer is 1 to 20 rice how.
13. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: described quantum dot layer comprises at least one item in silicon dioxide, silicon nitride, silica, aluminium oxide, magnesium oxide, strontium titanates, tantalum oxide, titanium dioxide, magnesium fluoride, zinc oxide, tin indium oxide, the silicon composition.
14. as each described manufacturing solar cell method in the claim 6 to 8, it is characterized in that: described method more comprises the following step:
Connect in the surface layer or produce a selectivity emitter layer afterwards forming described N.
15. a solar cell is characterized in that: comprise:
One matrix, this stromal surface are handled to reduce sun reflection coefficient;
One N connects surface layer, is formed on the described matrix;
One electricity slurry sublayer is formed and is formed at the top that described N connects surface layer by a plurality of metallics; And
One prevents to reflect cover layer, is formed at the top of described electricity slurry sublayer, to prevent reverberation.
16. solar cell as claimed in claim 15 is characterized in that: the processing of described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
17. solar cell as claimed in claim 15 is characterized in that: those metallics of described electricity slurry sublayer intersperse among described N and connect the whole surface of face.
18. solar cell as claimed in claim 17 is characterized in that: described electricity slurry sublayer comprises those metallics, and those metallics have a how penetration region (tunneling region) of rice of diameter 1 to 30.
19. solar cell as claimed in claim 17 is characterized in that: described electricity slurry sublayer comprises those metallics, and those metallics have a how optical diffraction district of rice of diameter 30 to 100.
20. solar cell as claimed in claim 15 is characterized in that: those metallics of described electricity slurry sublayer comprise the sieve aperture kenel that is formed by a plurality of holes.
21. solar cell as claimed in claim 20 is characterized in that: described electricity slurry sublayer comprises a metal particle layer in a sieve aperture kenel, and this sieve aperture kenel is coated the most nearly 30 those metallics of rice how of thickness.
22. as each described solar cell in the claim 15 to 21, it is characterized in that: described metallic comprises wherein at least one of gold, silver, copper, tweezer, chromium, iron, tungsten, molybdenum, zinc.
23. a method of making solar cell is characterized in that: comprise the following step:
Prepare a matrix;
The surface of handling described matrix is to reduce the reflection of incident light coefficient of this stromal surface;
Remove a phosphosilicate glass;
Form an electricity slurry sublayer, this electricity slurry sublayer is made up of a plurality of metallics and is formed at the top that this N connects surface layer; And
Form one and prevent to reflect cover layer.
24. manufacturing solar cell method as claimed in claim 23 is characterized in that: the step of handling described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
25. manufacturing solar cell method as claimed in claim 23 is characterized in that: the step that forms described electricity slurry sublayer is for disperseing those metallics to form a metal particle layer.
26. manufacturing solar cell method as claimed in claim 25 is characterized in that: the even dispersion diameter of step that forms described electricity slurry sublayer is 1 to the 30 described metallic of rice how.
27. manufacturing solar cell method as claimed in claim 23 is characterized in that: the step that forms described electricity slurry sublayer is for forming a metal particle layer in a sieve aperture kenel that is formed by a plurality of holes.
28. manufacturing solar cell method as claimed in claim 27 is characterized in that: the step that forms described electricity slurry sublayer is for forming a metal particle layer in a sieve aperture kenel, and this sieve aperture kenel is coated the most nearly 30 described metallics of rice how of thickness.
29. as the described manufacturing solar cell of claim 23 to 28 method, it is characterized in that: described metallic comprises wherein at least one of gold, silver, copper, tweezer, chromium, iron, tungsten, molybdenum, zinc.
30. as the described manufacturing solar cell of claim 25 to 28 method, it is characterized in that: described scanning sputter gun is used to disperse described metallic to starch the sublayer to form described electricity, and a particle density of each injection unit are is 10 13To 10 17Individual atom.
31. a solar cell is characterized in that: comprise:
One matrix, this stromal surface are handled to reduce sun reflection coefficient;
One layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by the described matrix of etching;
One N connects surface layer, is formed at the top of described matrix; And
One prevents to reflect cover layer, is formed at the top that described N connects face, to prevent reverberation.
32. solar cell as claimed in claim 31 is characterized in that: the processing of described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
33. solar cell as claimed in claim 31 is characterized in that: described layer of photonic crystals comprises a plurality of needle-like etched trench, and these a plurality of needle-like etched trench are formed by the etching of superficial makings layer.
34. solar cell as claimed in claim 33, it is characterized in that: the diameter of described needle-like etched trench is 30 to 200 rice how, and comprising several in the irregular needle-like part that the periodic lattice structure forms, those irregular needle-likes partly sizes are 0.1 to 2 micron.
35. as the described solar cell of claim 32 to 34, it is characterized in that: described superficial makings layer has the irregular part of several tapers, and the irregular part of those tapers has 4 to 10 microns interval.
36. a method of making solar cell is characterized in that: comprise the following step:
Prepare a matrix;
The surface of handling described matrix is to reduce the reflection of incident light coefficient of this stromal surface;
Form a layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by the described matrix of etching;
Form a N and connect surface layer on described matrix, and described layer of photonic crystals is formed at described matrix;
Remove a phosphosilicate glass; And
Form one and prevent to reflect cover layer.
37. manufacturing solar cell method as claimed in claim 36 is characterized in that: the step of handling described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
38. as each described manufacturing solar cell method in claim 36 and 37, it is characterized in that: the step that forms described layer of photonic crystals comprises to be etched with and forms a plurality of needle-like etched trench.
39. manufacturing solar cell method as claimed in claim 38 is characterized in that: etched step is for using reactive ion-etching and induction coupling electricity slurry method.
40. as each described manufacturing solar cell method in claim 36 and 37, it is characterized in that: the step that forms described layer of photonic crystals comprises:
Coat a constrictive type photoresistance and a sclerosis;
Form a shade type sample, this shade type sample has a plurality of type sample holes, and those type sample holes are corresponding with photonic crystal stratotype sample on the constrictive type photoresistance;
By described type sample hole to expose this matrix of described matrix and etching;
Remove described shade type sample; And
Connect surface layer in the matrix that described shade type sample removes to form a N by diffusion phosphorus.
41. manufacturing solar cell method as claimed in claim 40, it is characterized in that: the step that forms described shade type sample comprises utilizes a stamp module to form described type sample hole in described matrix, and this stamp module has the irregular part of corresponding described photonic crystal stratotype sample.
42. manufacturing solar cell method as claimed in claim 41 is characterized in that: the size of described shade type sample is 0.1 to 2 micron.
43. manufacturing solar cell method as claimed in claim 40 is characterized in that: the step of the described matrix of etching is radiation one ion beam.
44. manufacturing solar cell method as claimed in claim 40 is characterized in that: etched step is used reactive ion-etching and induction coupling electricity slurry method.
45. a solar cell is characterized in that: comprise:
One matrix, this stromal surface are handled to reduce sun reflection coefficient;
One layer of photonic crystals is formed at the surface of described matrix, and this layer of photonic crystals is made up of a plurality of trickle metallics and a plurality of quantum wire, and those quantum wires are formed at those trickle metallics bottoms with the incident light of reflection from inside;
One N connects surface layer, is formed on the described layer of photonic crystals; And
One prevents to reflect cover layer, is formed at the top that described N connects surface layer, to prevent reverberation.
46. solar cell as claimed in claim 45 is characterized in that: the processing of described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
47. solar cell as claimed in claim 45 is characterized in that: those quantum wires of described layer of photonic crystals are a needle-like kenel, and those quantum wires are formed in described metallic bottom by vapor deposited silicon.
48. as each described solar cell in the claim 45 to 47, it is characterized in that: the diameter of described metallic is 5 to 50 rice how.
49. as each described solar cell in the claim 45 to 47, it is characterized in that: the length of described quantum wire is 10 to 100 rice how.
50. a method of making solar cell is characterized in that: comprise the following step:
Prepare a matrix;
The surface of handling described matrix is to reduce the reflection of incident light coefficient of this stromal surface;
Form the surface of a layer of photonic crystals in described matrix, and this layer of photonic crystals is made up of a plurality of trickle metallics and a plurality of quantum wire, those quantum wires are formed at those trickle metallics bottoms with the incident light of reflection from inside;
Form a N and connect surface layer on described matrix, and described layer of photonic crystals is formed at this matrix;
Remove a phosphosilicate glass; And
Form one and prevent to reflect cover layer.
51. manufacturing solar cell method as claimed in claim 50 is characterized in that: the processing of described stromal surface comprises knits reason to form a superficial makings layer in described stromal surface.
52. as each described manufacturing solar cell method in claim 50 and 51, it is characterized in that: the step that forms described layer of photonic crystals comprises:
By spray a plurality of metallics in the surface of described matrix to form those trickle metallics; And
Vapor deposited silicon is in the bottom of those trickle metallics and produce those quantum wires.
53. manufacturing solar cell method as claimed in claim 52 is characterized in that: form trickle metallic step for the scanning sputter gun disperseing those metallics, and those metallic density of per unit area are 10 13To 10 17Individual atom.
54. a solar cell is characterized in that: comprise:
One matrix, this stromal surface are handled to reduce sun reflection coefficient;
One layer of photonic crystals, the lattice structure of tool one-period property arrangement, this lattice structure is formed by the described matrix of etching;
One quantum dot layer by vapour deposition, and forms a film substrate on described layer of photonic crystals top;
One N connects surface layer, is formed on described quantum dot layer top; And
One prevents to reflect cover layer, is formed at the top that described N connects surface layer, to prevent reverberation.
55. solar cell as claimed in claim 54 is characterized in that: described solar cell more comprises a selectivity emitter layer and connects on the surface layer in described N.
56. as the solar cell as described in the 54th of the claim, wherein this solar cell more comprises an electricity slurry sublayer, this electricity slurry sublayer is positioned at this N and connects surface layer top and be made up of a plurality of metallics.
57. a method of making solar cell is characterized in that: comprise the following step:
Prepare a matrix;
The surface of handling described matrix is to reduce the reflection of incident light coefficient of this stromal surface;
Form a layer of photonic crystals, and the lattice structure of this layer of photonic crystals tool one-period property arrangement, this lattice structure is formed by the described matrix of etching;
Form a quantum dot layer,, and form a film substrate on described layer of photonic crystals top by vapour deposition;
Form a N and connect surface layer on described matrix, and this quantum dot layer is formed at this matrix;
Remove a phosphosilicate glass, this phosphosilicate glass is formed at described N and connects on the surface layer;
Form an emitter layer, this emitter layer connects surface layer by the described N of heat treatment and gets; And
Form one and prevent to reflect cover layer on described emitter layer.
CN2010102624020A 2009-12-01 2010-08-25 Solar cell and method for manufacturing the same Expired - Fee Related CN102082184B (en)

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KR1020090125008A KR20110068161A (en) 2009-12-15 2009-12-15 Solar cell and manufacturing method of the same
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KR1020090125001A KR101079213B1 (en) 2009-12-15 2009-12-15 Solar cell and manufacturing method of the same
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CN110071423A (en) * 2018-01-22 2019-07-30 果尚志 The sub- laser aid of two-dimensional material plasma-based

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TWI492403B (en) * 2013-09-09 2015-07-11 Motech Ind Inc Solar cell, method for manufacturing the same and solar cell module

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CN103337530A (en) * 2013-06-09 2013-10-02 国电光伏有限公司 N-shaped efficient heterojunction battery and manufacturing method thereof
TWI495127B (en) * 2013-06-24 2015-08-01 Motech Ind Inc Solar cell, method of manufacturing the same and module comprising the same
CN110071423A (en) * 2018-01-22 2019-07-30 果尚志 The sub- laser aid of two-dimensional material plasma-based

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