CN101964373B - Double-junction solar cell of broad spectrum photovoltaic effect and preparation method thereof - Google Patents
Double-junction solar cell of broad spectrum photovoltaic effect and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a double-junction solar cell of broad spectrum photovoltaic effect and a preparation method thereof. The cell is provided with a light-facing surface second conductive type layer and a medium passivation layer in turn on the light-facing surface of a first conductive type substrate, wherein the surface of the medium passivation layer has a broad spectrum anti-reflection structure; the cell is provided with a backlight surface first conductive type layer and a backlight surface second conductive type layer in turn on the backlight surface of the first conductive type substrate; a first electrode formed on the light-facing surface second conductive type layer, a second electrode formed on the backlight surface second conductive type layer and a third electrode formed on the backlight surface first conductive type layer form the backlight surface first conductive type layer; and the same electrodes of the adjacent cells are interconnected to adjust the voltage and connected in parallel to form two-end output of a cell panel assembly. By using the double-junction solar cell, the photoelectric conversion spectrum of the cell is broadened so that the efficiency of the cell is improved.
Description
Technical field
The present invention relates to Si photoelectron material technical field, relate in particular to Double Junction Tandem Solar Cells of a kind of wide range photovoltaic effect and preparation method thereof.
Background technology
Silicon solar cell is the main body on the current photovoltaic market, and crystal-silicon solar cell is that transformation efficiency is the highest, and its world record is 24.7%.Crystal-silicon solar cell has very high quantum efficiency at 600～900nm wave band, more than 1100nm then because of energy gap can not absorb, 300 with the next energy that can't make full use of single-photon.Therefore, continue to improve the efficient of crystal-silicon solar cell, just must work hard at long wave and short-wave band.
The multiple level light absorption is a kind of light absorption method of wide range
[1], can realize in the Si material that the multiple level light absorption is that photovoltaic circle is very interested always.Nineteen fifty-nine Fan and Ramdas
[2]Report through the silicon of ion irradiation can be in the forbidden band the formation deep energy level; This deep energy level can reach infrared light generation light absorption and the photoelectric current of 4000nm to wavelength; Silicon through fast neutron width of cloth photograph has two tangible absworption peaks at 1800nm and 3900nm, and wherein the 1800nm absworption peak can extend to 1550nm and produce light absorption.
Calendar year 2001 Marzur has prepared surface micrometre-grade crystalline cone structure first in the research of ultrafast laser and Si surface action, this structure can wide spectrum anti-reflection sunlight, and its sulfur doping layer can absorb sunlight by wide range
[3]With the Si detector of this structure preparation, the infrared electro response reaches 1300nm under its room temperature.Impurity involved in the present invention can be with deeply can increase the absorption of Si to infrared light undoubtedly, and the battery of preparation must be widened the opto-electronic conversion spectrum like this.
On the other hand, Ge can be with band gap width can be with band gap width less than Si, can strengthen the wide range absorption of battery to sunlight greatly with two kinds of materials; Its n-Si/p-Ge heterojunction belongs to the second based semiconductor heterojunction again, and promptly valence band still is that conduction band does not all have spike at the heterojunction place, is very beneficial for the right separation in light induced electron-hole and transports separately.Si/Ge heterojunction involved in the present invention must form wide opto-electronic conversion spectrum, improves the conversion efficiency of Si photovoltaic cell greatly, makes it to be widely used.
List of references:
[1]Martin?A.Green，Solar?Cells：Operating?Principles，Technology，and?System?Applications，University?of?New?South?Wales?(1986).
[2]Fan?H?Y，Ramdas?A?K，“Infrared?Absorption?and?Photoconductivity?in?Irradiated?Silicon”，J.Appl.Phys.30：1127-1134(1959).
[3]C.Wu，et.al.，“Near-unity?below-band-gap?absorption?by?micro-structured?silicon”，Applied?Physics?Letters，78(13)：1850-52，2001.
[4]R.N.Bracewell，R.M.Swanson，“Silicon?photovoltaic?cells?in?TPV?conversion”，Interim?EPRI?ER-633，Electric?Power?Research?Institute，1978.
[5]C-H.Lin，“Si/Ge/Si?double?heterojunction?solar?cells”，Thin?Solid?Films，518，5255-5258，2010.
Summary of the invention
The technical problem that (one) will solve
In view of this, main purpose of the present invention is Double Junction Tandem Solar Cells that provides a kind of wide range photovoltaic effect and preparation method thereof, to improve the photoelectric conversion efficiency of photovoltaic cell.
(2) technical scheme
Be an aspect that achieves the above object; The invention provides a kind of Double Junction Tandem Solar Cells of wide range photovoltaic effect; This battery is on the side to light of first conductivity type substrate, to have a side to light second conductive type layer and a dielectric passivation layer in regular turn, and said dielectric passivation layer surface is the wide spectrum antireflection structure; Shady face in first conductivity type substrate has a shady face first conductive type layer and a shady face second conductive type layer in regular turn; Form first electrode on said side to light second conductive type layer, forming second electrode on said shady face second conductive type layer, on said shady face first conductive type layer, forming third electrode, constitute said Double Junction Tandem Solar Cells.
In the such scheme, have opening on wherein said shady face second conductive type layer, expose said shady face first conductive type layer, and form said third electrode above that.
In the such scheme, wherein said first conductivity type substrate is the first conduction type Si substrate; Said side to light second conductive type layer is to mix the Si of second conductive type impurity, Al
1-xGa
xAs, Ga
1-xIn
xThe P film, 0≤x＜1 wherein, its can with band gap be wider than or equal first conductivity type substrate can be with band gap.
In the such scheme, wherein said shady face first conductive type layer is the Si layer of heavily doped first conductive type impurity, or mixes the Si layer of the elementary sulfur S of VI family, selenium Se or tellurium Te, or mixes the Si layer of element zinc Zn of II family or cadmium Cd; Said VI family or the II family element of mixing, a part wherein can form deep energy level in the band gap middle part at Si, and another part is the instead type doping.
In the such scheme; Wherein said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb or GaSb film; It can with band gap equal or be narrower than the first conduction type Si substrate can band gap, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer.
In the such scheme, wherein said wide spectrum antireflection structure is surperficial crystalline cone array, perhaps is surperficial pyramid.
In the such scheme, wherein said shady face first conductive type layer is to mix the Si layer of VI family or II family element, and said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb, GaSb, Al
1-xGa
xAs or Ga
1-xIn
xThe P film, 0≤x＜1 wherein, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer.
In the such scheme; Wherein said shady face first conductive type layer is the Si layer of heavily doped first conductive type impurity, and described shady face second conductive type layer is to mix the Ge of second conductive type impurity, InAs, InSb or GaSb narrow gap semiconductor film.
In the such scheme, wherein said wide range is because difference can band gap absorb respectively and opto-electronic conversion sunlight; Said binode is because each battery has side to light pn knot and shady face pn knot, forms pnp or npn binode battery, and respectively by three electrode outputs, and second electrode has identical electrology characteristic with first electrode.
In the such scheme, the electrode of the same race of adjacent cell interconnects, and parallel connection forms the two ends output of battery panel components; Wherein:
Said electrode of the same race interconnects, and is that first electrode with each battery in the assembly interconnects, second electrode of each battery interconnects in the assembly, the third electrode of each battery interconnects in the assembly;
Said overall parallel connection forms the two ends output of battery panel components, and it is final parallelly connected that second electrode that is meant the battery component internal exchange General Logistics Department and first electrode of the battery component internal exchange General Logistics Department carry out, and export at the two ends that form battery panel components.
For achieving the above object on the other hand, the invention provides a kind of method for preparing the Double Junction Tandem Solar Cells of wide range photovoltaic effect, this method comprises:
On the first conductivity type substrate side to light, prepare wide spectrum antireflection structure and side to light second conductive type layer in regular turn;
On the first conductivity type substrate shady face, prepare shady face first conductive type layer and shady face second conductive type layer in regular turn;
To the heat treatment of annealing of said layers of material;
On said side to light second conductive type layer, prepare dielectric passivation layer;
On said side to light second conductive type layer, prepare first electrode, on shady face second conductive type layer, prepare second electrode, prepare third electrode, constitute said Double Junction Tandem Solar Cells in shady face first conductive type layer;
The identical electrodes that connects a plurality of batteries, parallel connection behind the adjustment voltage forms the two ends output of battery panel components.
In the such scheme, saidly on shady face first conductive type layer, prepare third electrode, comprising:
Adopt the method for wet method or dry etching, on shady face second conductive type layer, form opening, expose said shady face first conductive type layer; Adopt resistance heat evaporation or electron beam evaporation method on shady face first conductive type layer that said opening exposed, to prepare said third electrode.
In the such scheme, said wide spectrum antireflection structure and side to light second conductive type layer of on the first conductivity type substrate side to light, preparing in regular turn comprises:
In VI family or II family element atmosphere, adopt the ultra-short pulse laser irradiance method, preparation pointed cone array pattern on the first conduction type Si substrate side to light, and use chemical corrosion method, remove pointed cone surface doping layer; Perhaps adopt chemical corrosion method, the Si substrate surface prepares pyramid structure in (001);
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, on the said first conduction type Si substrate side to light wide spectrum antireflection structure, the Si layer of second conductive type impurity is mixed in preparation; Or the employing epitaxial growth method, on the said first conduction type Si substrate side to light wide spectrum antireflection structure, the Al of second conductive type impurity is mixed in preparation
1-xGa
xAs or Ga
1-xIn
xP film, wherein 0≤x＜1.
In the such scheme, said shady face first conductive type layer and shady face second conductive type layer of on the first conductivity type substrate shady face, preparing in regular turn comprises:
Adopt laser doping, ion to inject or both mixed methods, mix VI family or II family element, form the Si layer that deep energy level and instead type mix at the first conduction type Si substrate shady face; On the Si layer that mixes VI family or II family element, adopt the vacuum system epitaxial growth to mix Si, the Al of second conductive type impurity
1-xGa
xAs or Ga
1-xIn
xThe P film, 0≤x＜1 wherein, or adopt the vacuum system deposition to mix the amorphous silicon of second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer;
In the such scheme, said shady face first conductive type layer and shady face second conductive type layer of on the first conductivity type substrate shady face, preparing in regular turn comprises:
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, on the said first conduction type Si substrate shady face, prepare the Si layer of heavily doped first conductive type impurity; On the Si layer of heavily doped first conductive type impurity of this shady face, adopt the vacuum system epitaxial growth to mix Ge, InAs, InSb or the GaSb film of second conductive type impurity, its can with band gap be narrower than the first conduction type Si substrate can band gap.
In the such scheme, said shady face first conductive type layer and shady face second conductive type layer of on the first conductivity type substrate shady face, preparing in regular turn; Comprise:
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, prepare the Si layer of heavily doped first conductive type impurity at the first conduction type Si substrate shady face;
The method that adopts oxygen O ion to inject forms Ge/GeO on germanium Ge top layer
2/ Ge structure, promptly GOI is bonded to the GOI body structure surface on the Si layer of heavily doped first conductive type impurity of shady face, peels off the Ge substrate through heating means, removes GeO through chemical corrosion
2Layer then can form not have on the Si layer of heavily doped first conductive type impurity of shady face and pass through the Ge layer that mixes second conductive type impurity of dislocation.
In the such scheme, said to the layers of material heat treatment of annealing, be before electrode preparation, to carry out, annealing temperature between 300 ℃ to 1000 ℃, the time at 1 second in 60 minutes.
In the such scheme, the said ultra-short pulse laser irradiation that in VI family or II family element atmosphere, adopts, employed laser pulse width is less than 500 psecs, and pulse frequency is less than 10kHz, and pulse energy density is 1 to 10kJ/m
2Said VI family or II family element atmosphere are meant SF
6Atmosphere, or the powder coating atmosphere of sulphur S, selenium Se, tellurium Te, zinc Zn or cadmium Cd.
In the such scheme; Saidly mix VI family or II family element at the first conduction type Si substrate shady face; Inject or ion injects and adds the laser irradiation mode and carry out by laser doping, ion, concrete VI family and II family element atmosphere as previously mentioned, employed laser pulse width is less than 1 nanosecond; Pulse frequency is less than 10kHz, and pulse energy density is 0.5 to 5kJ/m
2And through 300 ℃ to 800 ℃ annealing 1 second to 60 minutes, activator impurity made the maximization of mixing of the instead type of VI family or II family element, and doped region surfacing or do not influence the surperficial dimpling of photoetching, rather than the pointed cone pattern.
In the such scheme; The preparation of said electrode; Be at the first conduction type laminar surface, the second conduction type laminar surface and the second conduction type laminar surface; Adopt resistance heat evaporation or electron beam evaporation method deposition of aluminum Al, chromium Cr, golden Au, tungsten W, titanium Ti, palladium Pd or silver-colored Ag metal material, and the heat treatment of annealing, Ohm contact electrode finally formed; If two electrode homonymies and metal are identical, adopt photoresist or SiO
2Isolate, prepare two electrodes simultaneously.
In the such scheme; Said surface bond; To two kinds of materials with atomically flating surface; In vacuum system, pressurize, make between the dangling bonds on two surfaces and get in touch, thereby under the condition of no medium, make two kinds of materials form the integral body connection through plasma activated surface and being lower than under 400 ℃ the temperature.
In the such scheme, further the electrode of the same race with adjacent cell interconnects, and adjustment voltage and parallel connection form the two ends output of battery panel components; Wherein:
Said electrode of the same race interconnects, and is that first electrode with each battery in the assembly interconnects, second electrode of each battery interconnects in the assembly, the third electrode of each battery interconnects in the assembly;
Said adjustment voltage and parallel connection; Form the two ends output of battery panel components; Be through series-parallel systems different between first electrode or through series-parallel systems different between second electrode or pass through inverter; Make the total voltage after second electrode interconnects in the battery component be equal to the total voltage after interior first electrode of battery component interconnects, final parallel connection forms the two ends output of battery panel components.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, utilizes the present invention, through the opto-electronic conversion of solid existing ultraviolet of battery side to light pn and visible light, carry out the opto-electronic conversion of infrared light, thereby widen the photovoltaic effect spectrum of battery on the whole, improve battery efficiency through shady face np knot.
2, utilize the present invention, can on the basis of crystal silicon photovoltaic cell, increase the absorption of Si IR through increasing the Si substrate thickness; Two pn knots have reduced the right diffusion length in light induced electron-hole again simultaneously, have avoided the contradiction of light absorption and opto-electronic conversion, thereby can improve the cell integrated photovoltaic effect of Si;
3, utilize the present invention, can add the Si solar cell, improving the short circuit current of its Si solar cell, thereby improve its photoelectric conversion efficiency deceiving the distinctive current gain of silicon.
Description of drawings
Fig. 1 is the binode battery structure schematic diagram of wide range photovoltaic effect provided by the invention;
Fig. 2 is that the binode battery electrode connects sketch map in the battery panel components provided by the invention, and wherein A is gathering of electrode a, and B is gathering of electrode b, and C is gathering of electrode c, and M is an inverter, and A ' is M output;
Fig. 3 is first kind of binode battery structure figure under the technology path;
Fig. 4 be second kind with the third technology path under binode battery structure figure;
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
Fig. 1 is the binode battery structure schematic diagram of wide range photovoltaic effect provided by the invention; This battery is on the side to light of first conductivity type substrate, to have a side to light second conductive type layer and a dielectric passivation layer in regular turn, and said dielectric passivation layer surface is the wide spectrum antireflection structure; Shady face in first conductivity type substrate has a shady face first conductive type layer and a shady face second conductive type layer in regular turn; Form first electrode on said side to light second conductive type layer, forming second electrode on said shady face second conductive type layer, on said shady face first conductive type layer, forming third electrode, constitute said Double Junction Tandem Solar Cells.
Wherein, have opening on said shady face second conductive type layer, expose said shady face first conductive type layer, and form said third electrode above that; And second electrode has identical electrology characteristic with first electrode.
Wherein, said first conductivity type substrate is the first conduction type Si substrate; Said side to light second conductive type layer is to mix the Si of second conductive type impurity, Al
1-xGa
xAs, Ga
1-xIn
xThe P film, 0≤x＜1 wherein, its can with band gap be wider than or equal first conductivity type substrate can be with band gap;
Wherein, Said shady face first conductive type layer is the Si layer of heavily doped first conductive type impurity; Or mix the Si layer of the elementary sulfur S of VI family, selenium Se or tellurium Te, or mix the Si layer of element zinc Zn of II family or cadmium Cd, said VI family or the II family element of mixing; A part wherein can form deep energy level in the band gap middle part at Si, and another part is the instead type doping.
Wherein, Said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb or GaSb film; It can with band gap equal or be narrower than the first conduction type Si substrate can band gap, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer.
Wherein, said wide spectrum antireflection structure is surperficial crystalline cone array, perhaps is surperficial pyramid.
Wherein, said wide range is because difference can band gap absorb respectively and opto-electronic conversion sunlight; Said binode is because each battery has side to light pn knot and shady face pn knot; Form pnp or npn binode battery; Absorb the light (like ultraviolet, visible light) of shorter wavelength with side to light pn knot; Absorb infrared light with substrate shady face np knot, and both photo-generated carriers are exported, respectively by three electrodes outputs.
Fig. 2 is that the binode battery electrode connects sketch map in the battery panel components provided by the invention, and this battery further interconnects a plurality of adjacent this battery electrodes of the same race, and adjustment voltage and parallel connection form the two ends output of battery panel components; Wherein: said electrode of the same race interconnects, be with each battery first electrode a in the assembly interconnect, each battery second electrode b interconnects in the assembly, each battery third electrode c interconnects in the assembly; Said adjustment voltage and parallel connection; Form the two ends output of battery panel components; Be through series-parallel systems different between the first electrode a, through series-parallel systems different between the second electrode b or through inverter, make the total voltage V after the second electrode b interconnects in the assembly
B=∑ V
bBe equal to the total voltage V after the first electrode a interconnects in the assembly
A=∑ V
a, final parallel connection forms the two ends output of battery panel components.
Fig. 3 is the structure chart of first kind of binode battery under the technology path; Wherein said first conductivity type substrate is the first conduction type Si substrate 1; Said side to light second conductive type layer is to mix the Si layer 2 of second conductive type impurity, and said side to light dielectric layer is SiO
2Or SiN film 5, said shady face first conductive type layer is to mix the Si layer 3 of VI family or II family element, said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb, GaSb, Al
1-xGa
xAs or Ga
1-xIn
xP film 4,0≤x＜1 wherein, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer 4; Said first electrode 6 is positioned on second conductive type layer 2 of dielectric passivation layer opening part; Said second electrode 7 is positioned on shady face second conductive type layer 4, and said third electrode 8 is positioned on shady face first conductive type layer 3 of shady face second conductive type layer 4 opening parts.
Because VI family or II family element are introduced deep energy level in the crystalline silicon forbidden band, therefore formed three grades or multistage light absorption, make portions of electronics after twice light absorption, transit to conduction band; Owing to the increase of this deep energy level density, might form the deep energy level subband, thereby the photo-generated carrier on the deep energy level subband is directly exported again.
Because VI family or II family element form instead type and mix in crystalline silicon, have two peripheral electrons, and ionization energy is little, therefore form the avalanche type enlarge-effect easily.
Because it is higher to mix the concentration of VI family or II family element, the pn knot of therefore forming, low substrate one side of The built-in electric field deflection concentration by doped layer and substrate.In order to make internal electric field cover the high-concentration dopant layer, must add a high concentration inversion layer, form the pn knot at its interface.
The manufacture method of the binode battery under this technology path comprises the steps:
In VI family or II family element atmosphere, adopt the ultra-short pulse laser irradiance method, preparation pointed cone array pattern on the first conduction type Si substrate, 1 side to light, and, form the surface micro-structure of wide spectrum anti-reflection with chemical corrosion method removal pointed cone surface doping layer; Or the employing chemical corrosion method, prepare pyramid structure at the first conduction type Si substrate, 1 side to light.
Adopt ion to inject or thermal diffusion or epitaxy method, on the first conduction type Si substrate, 1 side to light wide spectrum antireflection structure, the Si layer 2 of second conductive type impurity is mixed in preparation, constitutes side to light pn knot with the first conduction type Si substrate;
Adopt laser doping, ion to inject perhaps first ion and inject the method for back laser irradiation, mix VI family or II family element, form the Si layer 3 that deep-level impurity and instead type mix at the first conduction type Si substrate shady face; On 3, adopt the vacuum system epitaxial growth to mix Si, Ge, InAs, InSb, GaSb, the Al of second conductive type impurity
1-xGa
xAs or Ga
1-xIn
xP film 4,0≤x＜1 wherein, or adopt the vacuum system deposition to mix the amorphous silicon of second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer 4,
In 300 ℃ to 1000 ℃ scopes, adopt method for annealing that Si substrate and said layers of material thereof are heat-treated, with the impurity in the active material;
On side to light second conductive type layer 2, adopt vacuum system deposition SiO
2Or SiN thin layer 5;
Adopt the method for wet method and dry etching, on shady face second conductive type layer 4, form opening, expose shady face first conductive type layer 3; Adopt resistance heat evaporation or electron beam evaporation method, preparation ohmic contact third electrode 8 on shady face first conductive type layer 3 that said opening exposed;
Adopt resistance heat evaporation or electron beam evaporation method, at side to light SiO
2Or preparation ohmic contact first electrode 6 on second conductive type layer 2 of SiN thin layer opening part; Preparation ohmic contact second electrode 7 on shady face second conductive type layer 4;
Fig. 4 is second kind of binode battery structure figure under the technology path, and wherein said first conductivity type substrate is the first conduction type Si substrate 1, and said side to light second conductive type layer is to mix the Si layer 2 of second conductive type impurity, and said side to light dielectric layer is SiO
2Or SiN film 5, described shady face first conductive type layer is the Si layer 9 of heavily doped first conductive type impurity, described shady face second conductive type layer is to mix the Ge of second conductive type impurity, InAs, InSb or GaSb narrow gap semiconductor film 10; Said first electrode 6 is positioned at side to light SiO
2Or on second conductive type layer 2 of SiN thin layer opening part, said second electrode 11 is positioned on second conductive type layer 10, and said third electrode 12 is positioned on first conductive type layer 9 of shady face second conductive type layer 10 opening parts.
Prepare the arrowband material at the substrate shady face, to absorb infrared light; And the infrared light of tying absorption through shady face pn converts photo-generated carrier and output to.Shady face Si/Ge is the second based semiconductor heterojunction, and no spike potential barrier is easy to transporting of photo-generated carrier especially.
The manufacture method of the binode battery under this technology path comprises the steps:
In VI family element atmosphere, adopt the ultra-short pulse laser irradiance method, preparation pointed cone array pattern on the first conduction type Si substrate side to light, and use chemical corrosion method, and remove pointed cone surface doping layer, form the surface micro-structure of wide spectrum anti-reflection; Adopt chemical corrosion method, prepare the wide spectrum antireflection structure at the first conduction type Si substrate, 1 side to light;
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, the Si layer 2 of second conductive type impurity is mixed in preparation on the first conduction type Si substrate, 1 side to light wide spectrum antireflection structure, constitutes side to light pn knot with the first conduction type Si substrate;
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, prepare the Si layer 9 of heavily doped first conductive type impurity at the first conduction type Si substrate, 1 shady face;
Adopt vacuum system, on the Si layer 9 of heavily doped first conductive type impurity of shady face, Ge, InAs, InSb or the GaSb narrow gap semiconductor film 10 of second conductive type impurity mixed in epitaxial growth, constitutes shady face pn knot with the first conduction type Si substrate; Adopt the method for wet method and dry etching, shady face second conductive type layer 10 is formed opening, expose the Si layer 9 of heavily doped first conductive type impurity;
In 300 ℃ to 1000 ℃ scopes, adopt method for annealing that Si substrate and said layers of material thereof are heat-treated, with the impurity in the active material;
On the side to light second conduction type Si layer 2, adopt vacuum system deposition SiO
2Or SiN thin layer 5;
Adopt resistance heat evaporation or electron beam evaporation method, at side to light SiO
2Or preparation ohmic contact first electrode 6 on the second conduction type Si layer 2 of SiN film opening part; Preparation ohmic contact second electrode 11 on the shady face second conduction type film 10, preparation ohmic contact third electrode 12 on the Si layer 9 of heavily doped first conductive type impurity of the shady face second conduction type film opening part;
Fig. 4 also is the binode battery structure figure under the third technology path, wherein about the argumentation of battery structure not in this repetition.
The manufacture method of the binode battery under this technology path comprises the steps:
In VI family element atmosphere, adopt the ultra-short pulse laser irradiance method, preparation pointed cone array pattern on the first conduction type Si substrate, 1 side to light, and use chemical corrosion method, and remove pointed cone surface doping layer, form the surface micro-structure of wide spectrum anti-reflection; Or the employing chemical corrosion method, prepare pyramid structure at the first conduction type Si substrate, 1 side to light;
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, the Si layer 2 of second conductive type impurity is mixed in preparation on the first conduction type Si substrate, 1 side to light wide spectrum antireflection structure, constitutes side to light pn knot with the first conduction type Si substrate;
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, prepare the Si layer 9 of heavily doped first conductive type impurity at the first conduction type Si substrate, 1 shady face;
The method that adopts oxygen O ion to inject forms Ge/GeO on germanium Ge top layer
2/ Ge structure, promptly GOI is bonded to the GOI body structure surface on the Si layer of heavily doped first conductive type impurity of shady face, and peels off the Ge substrate through heating means, corrodes GeO with chemical method
2, then can on the Si layer of heavily doped first conductive type impurity of shady face, form not have and pass through the second conduction type Ge layer 10 of dislocation, constitute shady face pn knot with the shady face first conduction type Si layer;
Adopt the method for wet method and dry etching, second conductive type layer 10 is formed opening, expose the Si layer 9 of heavily doped first conductive type impurity;
In 300 ℃ to 1000 ℃ scopes, adopt method for annealing that Si substrate and said layers of material thereof are heat-treated, with the impurity in the active material;
On the side to light second conduction type Si layer 2, adopt vacuum system deposition SiO
2Or SiN film 5;
Adopt resistance heat evaporation or electron beam evaporation method at side to light SiO
2Or preparation ohmic contact first electrode 6 on the second conduction type Si layer 2 of SiN film opening part; Preparation ohmic contact second electrode 11 on the shady face second conduction type Ge film 10, preparation ohmic contact third electrode 12 on the Si layer 9 of heavily doped first conductive type impurity of the shady face second conduction type film opening part;
In VI family or II family element atmosphere, adopt the ultra-short pulse laser irradiation first conduction type Si substrate described in Fig. 3 and Fig. 4, the laser pulse width of use is less than 500 psecs, and pulse frequency is less than 10kHz, and pulse energy density about 1 is to 10kJ/m
2, form pyramid surface micrometer structure at the upper and lower surfaces of Si substrate; Said VI family element is meant sulphur S, selenium Se or tellurium Te, and said II family element is meant zinc Zn or cadmium Cd.The said employing chemical corrosion first conduction type Si substrate is to adopt NaOH and C
2H
5The side to light of the OH mixed-alkali solvent corrosion first conduction type Si substrate, the micrometer structure on the side to light formation pyramid surface of the first conduction type Si substrate.
Adopting annealing heat treatment described in Fig. 3 and Fig. 4, is in 300 ℃ to 1000 ℃ scopes, the battery layers of material to be heated 1 second to 60 minutes, activates the impurity in the layers of material.
First, second and third electrode described in Fig. 3 and Fig. 4 adopt resistance heat evaporation or electron beam evaporation method to prepare at other semiconductor surface deposition of aluminum Al, chromium Cr, golden Au, tungsten W, titanium Ti, palladium Pd or silver-colored Ag metal materials such as the Si of heavily doped impurity, Ge.
Case study on implementation
The method of the crystalline silicon Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect shown in Figure 3 of being based on present embodiment realizes that concrete technical process is following:
Preparation wide spectrum antireflection structure on the first conduction type Si substrate, 1 side to light; Be in sulphur S, selenium Se, tellurium Te element atmosphere, to adopt ultrashort pulse laser scan irradiation Si surface; Its pulse duration is less than 100 psecs, and pulse frequency is less than 5kHz, the about 1-10kJ/m of energy density
2, make the Si surface form the crystalline cone pattern of micron dimension, thereby reach the purpose of wide spectrum anti-reflection incident light.Adopt NaOH and C
2H
5OH mixed-alkali solvent corrosion Si surface because it has different corrosion rates to each (hkl) crystal face of Si, thereby can form the pyramid surface texture;
On the first conduction type Si substrate side to light wide spectrum antireflection structure, adopt thermal diffusion, ion injection, laser doping, epitaxial growth method to prepare second conductive type layer 2, thereby form the pn knot with the first conduction type Si substrate;
Mix the Si layer 3 of VI family or II family element in the preparation of the first conduction type Si substrate shady face; The main ion of sulphur S, selenium Se, tellurium Te, zinc Zn, cadmium Cd element that adopts injects or thermal diffusion; These impurity form instead type and mix in Si; And the introducing deep energy level, the deep energy level of high concentration might form subband;
On the shady face first conduction type Si layer 3, adopt the vacuum system epitaxial growth to mix Si, Ge, InAs, InSb, GaSb, the Al of second conductive type impurity
1-xGa
xAs or Ga
1-xIn
xP film 4,0≤x＜1 wherein, or adopt the vacuum system deposition to mix the amorphous silicon a-Si:H of second conductive type impurity, receive crystal silicon nc-Si, microcrystal silicon μ c-Si thin layer 4.
In 300 ℃ to 1000 ℃ scopes, to 1 second to 60 minutes annealing heat treatment of doping Si sheet heating, to activate impurity among the Si;
On the side to light second conduction type Si layer 2, adopt the PECVD method to prepare SiO
2Or SiN film 5;
Connection in the battery panel components between the battery is to carry out with the connection between the similar electrode of battery, as each battery first electrode a in the assembly is interconnected, each battery second electrode b interconnects in the assembly, each battery third electrode c interconnects in the assembly; Through series-parallel systems different between the first electrode a, through series-parallel systems different between the second electrode b or through inverter, make the total voltage V after the second electrode b interconnects in the assembly
B=∑ V
bBe equal to the total voltage V after the first electrode a interconnects in the assembly
A=∑ V
a, final parallel connection forms the two ends output of battery panel components.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (20)
1. the Double Junction Tandem Solar Cells of a wide range photovoltaic effect; It is characterized in that; This battery is on the side to light of the first conduction type silicon substrate, to have a side to light second conductive type layer and a dielectric passivation layer in regular turn, and said dielectric passivation layer surface is the wide spectrum antireflection structure; Shady face at the first conduction type silicon substrate has a shady face first conductive type layer and a shady face second conductive type layer in regular turn; Form first electrode on said side to light second conductive type layer, forming second electrode on said shady face second conductive type layer, on said shady face first conductive type layer, forming third electrode, constitute said Double Junction Tandem Solar Cells; Have opening on wherein said shady face second conductive type layer, expose said shady face first conductive type layer, and on shady face first conductive type layer that said opening exposed, form said third electrode.
2. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1, it is characterized in that wherein said side to light second conductive type layer is to mix the Si of second conductive type impurity, Al
1-xGa
xAs or Ga
1-xIn
xThe P film, 0≤x＜1 wherein, its can with band gap be wider than or equal the first conduction type silicon substrate can be with band gap.
3. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1; It is characterized in that; Wherein said shady face first conductive type layer is the Si layer of heavily doped first conductive type impurity; Or mix the Si layer of the elementary sulfur S of VI family, selenium Se or tellurium Te, or mix the Si layer of element zinc Zn of II family or cadmium Cd; Said VI family or the II family element of mixing, a part wherein can form deep energy level in the band gap middle part at Si, and another part is the instead type doping.
4. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1; It is characterized in that; Wherein said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb or GaSb film; It can with band gap equal or be narrower than the first conduction type silicon substrate can band gap, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer.
5. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1, it is characterized in that wherein said wide spectrum antireflection structure is surperficial crystalline cone array, perhaps is surperficial pyramid.
6. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1; It is characterized in that; Wherein said shady face first conductive type layer is to mix the Si layer of VI family or II family element, and said shady face second conductive type layer is to mix the Si of second conductive type impurity, Ge, InAs, InSb, GaSb, Al
1-xGa
xAs or Ga
1-xIn
xThe P film, 0≤x＜1 wherein, or for the amorphous silicon that mixes second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer.
7. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1; It is characterized in that; Wherein said shady face first conductive type layer is the Si layer of heavily doped first conductive type impurity, and described shady face second conductive type layer is to mix the Ge of second conductive type impurity, InAs, InSb or GaSb narrow gap semiconductor film.
8. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1, it is characterized in that said wide range is because difference can band gap absorb respectively and opto-electronic conversion sunlight; Said binode is because each battery has side to light pn knot and shady face pn knot, forms pnp or npn binode battery, and respectively by three electrode outputs, and second electrode has identical electrology characteristic with first electrode.
9. according to the Double Junction Tandem Solar Cells of each described wide range photovoltaic effect in the claim 1, it is characterized in that the electrode of the same race of adjacent cell interconnects, parallel connection forms the two ends output of battery panel components; Wherein:
Said electrode of the same race interconnects, and is that first electrode with each battery in the assembly interconnects, second electrode of each battery interconnects in the assembly, the third electrode of each battery interconnects in the assembly;
Said parallel connection forms the two ends output of battery panel components, and it is final parallelly connected that second electrode that is meant the battery component internal exchange General Logistics Department and first electrode of the battery component internal exchange General Logistics Department carry out, and export at the two ends that form battery panel components.
10. a method for preparing the Double Junction Tandem Solar Cells of wide range photovoltaic effect is characterized in that, this method comprises:
On the first conduction type silicon substrate side to light, prepare wide spectrum antireflection structure and side to light second conductive type layer in regular turn;
On the first conduction type silicon substrate shady face, prepare shady face first conductive type layer and shady face second conductive type layer in regular turn;
To the heat treatment of annealing of said layers of material;
On said side to light second conductive type layer, prepare dielectric passivation layer;
On said side to light second conductive type layer preparation first electrode, on shady face second conductive type layer preparation second electrode, on shady face first conductive type layer, prepare third electrode, constitute said Double Junction Tandem Solar Cells;
The identical electrodes that connects a plurality of batteries, parallel connection behind the adjustment voltage forms the two ends output of battery panel components;
Wherein on shady face first conductive type layer, prepare third electrode, comprising: adopt the method for wet method or dry etching, on shady face second conductive type layer, form opening, expose said shady face first conductive type layer; Adopt resistance heat evaporation or electron beam evaporation method on shady face first conductive type layer that said opening exposed, to prepare said third electrode.
11. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 10 is characterized in that, said wide spectrum antireflection structure and side to light second conductive type layer of on the first conduction type silicon substrate side to light, preparing in regular turn comprises:
In VI family or II family element atmosphere, adopt the ultra-short pulse laser irradiance method, preparation pointed cone array pattern on the first conduction type silicon substrate side to light, and use chemical corrosion method, remove pointed cone surface doping layer; Perhaps adopt chemical corrosion method, the Si substrate surface prepares pyramid structure in (001);
Adopt ion injection, thermal diffusion, laser doping or epitaxially grown method, on the said first conduction type silicon substrate side to light wide spectrum antireflection structure, the Si film of second conductive type impurity is mixed in preparation; Or adopt epitaxially grown method, on the said first conduction type silicon substrate side to light wide spectrum antireflection structure, the Al of second conductive type impurity is mixed in preparation
1-xGa
xAs or Ga
1-xIn
xP film, wherein 0≤x＜1.
12. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 10; It is characterized in that; Said shady face first conductive type layer and shady face second conductive type layer of on the first conduction type silicon substrate shady face, preparing in regular turn comprises:
Adopt laser doping, ion to inject or both mixed methods, mix VI family or II family element, form the Si layer that deep energy level and instead type mix at the first conduction type silicon substrate shady face; On the Si layer that mixes VI family or II family element, adopt the vacuum system epitaxial growth to mix Si, the Al of second conductive type impurity
1-xGa
xAs or Ga
1-xIn
xThe P film, 0≤x＜1 wherein, or adopt the vacuum system deposition to mix the amorphous silicon of second conductive type impurity, receive crystal silicon or microcrystal silicon thin layer;
13. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 10; It is characterized in that; Said shady face first conductive type layer and shady face second conductive type layer of on the first conduction type silicon substrate shady face, preparing in regular turn comprises:
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, prepare the Si layer of heavily doped first conductive type impurity at the first conduction type silicon substrate shady face; On the Si layer of heavily doped first conductive type impurity of shady face, adopt the vacuum system epitaxial growth to mix Ge, InAs, InSb or the GaSb film of second conductive type impurity, its can with band gap be narrower than the first conduction type silicon substrate can band gap.
14. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 10 is characterized in that, said shady face first conductive type layer and shady face second conductive type layer of on the first conduction type silicon substrate shady face, preparing in regular turn; Comprise:
Adopt ion injection, thermal diffusion, laser doping or epitaxial growth method, prepare the Si layer of heavily doped first conductive type impurity at the first conduction type silicon substrate shady face;
The method that adopts oxygen O ion to inject forms Ge/GeO on germanium Ge top layer
2/ Ge structure, promptly GOI is bonded to the GOI body structure surface on the Si layer of heavily doped first conductive type impurity of shady face, peels off the Ge substrate through heating means, removes GeO through chemical corrosion method
2Layer then forms not have on the Si layer of heavily doped first conductive type impurity of shady face and passes through the Ge layer that mixes second conductive type impurity of dislocation.
15. method according to the Double Junction Tandem Solar Cells of each the described preparation wide range photovoltaic effect in the claim 11 to 14; It is characterized in that; Said to the layers of material heat treatment of annealing; Be to carry out before the electrode preparation, annealing temperature between 300 ℃ to 1000 ℃, the time at 1 second in 60 minutes.
16. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 11; It is characterized in that; The said ultra-short pulse laser irradiation that in VI family or II family element atmosphere, adopts; Employed laser pulse width is less than 500 psecs, and pulse frequency is less than 10kHz, and pulse energy density is 1 to 10kJ/m
2Said VI family or II family element atmosphere are meant SF
6Atmosphere, or the powder coating atmosphere of sulphur S, selenium Se, tellurium Te, zinc Zn or cadmium Cd.
17. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 12; It is characterized in that; Saidly mix VI family or II family element at the first conduction type silicon substrate shady face; Add the laser irradiation mode by laser doping, ion injection or ion injection and carry out, concrete VI family and II family element atmosphere are meant SF
6Atmosphere, or the powder coating atmosphere of sulphur S, selenium Se, tellurium Te, zinc Zn or cadmium Cd, employed laser pulse width be less than 1 nanosecond, and pulse frequency is less than 10kHz, and pulse energy density is 0.5 to 5kJ/m
2And through 300 ℃ to 800 ℃ annealing 1 second to 60 minutes, activator impurity made the maximization of mixing of the instead type of VI family or II family element, and doped region surfacing or do not influence the surperficial dimpling of photoetching, rather than the pointed cone pattern.
18. method according to the Double Junction Tandem Solar Cells of each described preparation wide range photovoltaic effect in the claim 10 to 14; It is characterized in that; The preparation of said electrode is at the side to light first conduction type laminar surface, the shady face first conduction type laminar surface and the second conduction type laminar surface, adopts resistance heat evaporation or electron beam evaporation method deposition of aluminum Al, chromium Cr, golden Au, tungsten W, titanium Ti, palladium Pd or silver-colored Ag metal material; And the heat treatment of annealing finally forms Ohm contact electrode; Because two electrode homonymies of shady face and metal are identical, so adopt photoresist or SiO
2Isolate, prepare two electrodes simultaneously.
19. the method for the Double Junction Tandem Solar Cells of preparation wide range photovoltaic effect according to claim 14; It is characterized in that; Said surface bond to two kinds of materials with atomically flating surface, pressurizes through the plasma activated surface and being lower than under 400 ℃ the temperature in vacuum system; Make between the dangling bonds on two surfaces and get in touch, thereby under the condition of no medium, make two kinds of materials form whole the connection.
20. the Double Junction Tandem Solar Cells of wide range photovoltaic effect according to claim 10 is characterized in that, further the electrode of the same race with adjacent cell interconnects, and adjustment voltage and parallel connection form the two ends output of battery panel components; Wherein:
Said electrode of the same race interconnects, and is that first electrode with each battery in the assembly interconnects, second electrode of each battery interconnects in the assembly, the third electrode of each battery interconnects in the assembly;
Said adjustment voltage and parallel connection; Form the two ends output of battery panel components; Be through series-parallel systems different between first electrode or through series-parallel systems different between second electrode or pass through inverter; Make the total voltage after second electrode interconnects in the assembly be equal to the total voltage after interior first electrode of assembly interconnects, final parallel connection forms the two ends output of battery panel components.
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| CN102496638A (en) * | 2011-11-28 | 2012-06-13 | 中国科学院半导体研究所 | Deep-level impurity-doped crystalline silicon infrared detector and preparation method thereof |
| CN103165721B (en) * | 2013-04-01 | 2016-08-03 | 南通大学 | A kind of manufacturing process of double-junction solar battery in parallel |
| CN103247675B (en) * | 2013-05-23 | 2016-07-13 | 哈尔滨工业大学 | Possesses the heterojunction triode of opto-electronic conversion and enlarging function |
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