CN104393120B - Preparation method and purpose of top cell P type layer of amorphous silicon germanium thin-film solar cell - Google Patents
Preparation method and purpose of top cell P type layer of amorphous silicon germanium thin-film solar cell Download PDFInfo
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- CN104393120B CN104393120B CN201410556353.XA CN201410556353A CN104393120B CN 104393120 B CN104393120 B CN 104393120B CN 201410556353 A CN201410556353 A CN 201410556353A CN 104393120 B CN104393120 B CN 104393120B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 29
- 239000010409 thin film Substances 0.000 title claims abstract description 24
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 229910000085 borane Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000010408 film Substances 0.000 claims description 10
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H01L31/028—
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- H01L31/035272—
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- H01L31/076—
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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
- 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
- Y02E10/548—Amorphous 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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- Sustainable Energy (AREA)
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Abstract
The invention discloses a preparation method and purpose of a top cell P type layer of an amorphous silicon germanium thin-film solar cell. According to the method, a P type layer of a top cell is prepared by a radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) method; and reactant gas includes hydrogen, silane, and borane. During deposition, gas flow volume proportion of the hydrogen to silane to borane is maintained to be 150 to 200 : 1 : 3 to 8; the borane is borane- hydrogen mixed gas, wherein the borane volume concentration is 0.5%; the air pressure is 160 to 220 Pa; the preparation temperature is within 100 DEG C; the power density inside the cavity is over 300mW/cm＜2＞; and the band gap width of the P type layer is over 2.0 eV. With the P type layer, the top cell can obtain the high open-circuit voltage and the short-circuit current density can be reduced properly and thus the short-circuit currents generated by the top cells in all sub cells of dual-junction and three-junction cells are the lowest ones, thereby forming a top cell current limitation effect. Therefore, current matching among all sub cells and the fill factors of the integrated cells can be effectively improved, thereby improving the photoelectric conversion efficiency of the dual-junction and three-junction amorphous silicon germanium thin-film solar cells.
Description
Technical field
The invention belongs to silicon-based thin film solar cell field, it is related to a kind of amorphous silicon germanium thin film solar cell；Specifically,
It is related to a kind of Preparation method and use for binode and the new p layer of three junction amorphous silicon germanium thin film solar cell top batteries.
Background technology
In various hull cells, non-crystalline silicon (a-si:h) thin film solar cell is to develop the earliest, thin film of most study
Battery.Due to amorphous silicon thin-film materials greater band gap itself, insufficient to long wave light absorbs in solar spectrum, limit battery effect
The raising further of rate.In order to widen the effective uptake region to solar spectrum, people will be relatively low for band gap width and continuously may be used
Amorphous silicon germanium (a-sige:h) materials application adjusted is in battery it is proposed that non-crystalline silicon/amorphous silicon germanium (a-si:h/a-sige:h)
Binode thin film solar cell and non-crystalline silicon/amorphous silicon germanium/amorphous silicon germanium (a-si:h/a-sige:h/a-sige:h) three knot are thin
The design of film solar cell.Binode and three junction amorphous silicon germanium thin film solar cells can effectively widen battery to solar spectrum
Effective uptake region, the top sub- cell band gap of battery non-crystalline silicon is the widest, and it absorbs higher light, intermediate cell and the bottom of short wavelength's energy
Battery absorbs the relatively low light of long wave strong point energy successively.
Due to the structure of the series connection between each sub- battery, the final electric current output of battery that son minimum by producing electric current
Battery determines, the currents match between therefore each sub- battery just seems particularly significant, is preparing binode and three junction amorphous silicon germaniums electricity
Chi Shi, the problem existing is mainly sunlight and is mainly absorbed by top battery, and residue is effectively absorbed by intermediate cell and bottom battery
Light is not enough, thus causing top battery current higher, and middle battery and bottom battery current are relatively low, ultimately limit total electric current defeated
Go out.If reducing the thickness of top battery simply, the open-circuit voltage easily causing top battery reduces, thus leading to the total electricity of battery
Drops, impact cell photoelectric conversion efficiency improves.
Content of the invention
The purpose of the present invention is for above-mentioned problem, provides one kind to be applied to binode and three junction amorphous silicon germanium films
The new p layer of solar cell top battery, when preparing the p layer of binode and three junction amorphous silicon germanium thin film solar cell top batteries, phase
Ratio, in the p layer of bottom battery and middle subcell, adopts higher hydrogen dilution ratio, higher power and air pressure and relatively low sinking
Accumulated temperature degree, the higher p-type nanometer silicon layer of formation of deposits band gap width.Thus so that the top battery of preparation obtains higher open circuit
Voltage appropriateness its short-circuit current density of reduction, make the short circuit current that top battery produces in binode and each sub- battery of three junction batteries
Minimum, thus forming " top battery current limits " effect, such design can effectively improve the electric current between each sub- battery
Join and integral battery door fill factor, curve factor, thus improving binode and the photoelectric transformation efficiency of three junction amorphous silicon germanium hull cells.
For reaching above-mentioned purpose, the invention provides a kind of preparation of amorphous silicon germanium thin film solar cell top cell p type layer
Method, the method is the p-type doping using plasma reinforced chemical vapour deposition (rf-pecvd) method deposition preparation top battery
Layer, reacting gas be hydrogen, silane, borine, preparation temperature within 100 DEG C, the gas stream of hydrogen, silane and borine during deposition
Amount volume ratio is maintained at 150～200:1:3～8, and wherein, borine is with diluted in hydrogen, and volumetric concentration is 0.5% borine hydrogen
Oxygen mixture；Chamber internal gas pressure is maintained at 160-220 pa, and within the chamber power density is in 300 mw/cm2More than；Described p
Type doped layer band gap width is in 2.0 more than ev.Described power density is higher, and within the specific limits, film growth rate is faster,
Quality of forming film can accordingly reduce, and increase with the pollution such as within the chamber bloom simultaneously, be not therefore the trend that the higher the better；But it is
Prepare p-type layer of the presently claimed invention, should be maintained at 300 mw/cm2More than.In addition, band gap width is in 2.0 more than ev,
It has been a very high value, and because material self character is limited, this band gap width value can not arbitrarily continue to increase.
Above-mentioned preparation method, wherein, described preparation temperature is 70～80 DEG C.
Above-mentioned preparation method, wherein, during deposition, chamber internal gas pressure is maintained at 200 pa(2.0 mbar).
Above-mentioned preparation method, wherein, described p-type doped layer thickness is 15～30nm.
Present invention also offers a kind of p-type layer of said method preparation, wherein, this p-type doped layer band gap width is 2.0
More than ev, thickness is 15～30nm.
Present invention also offers a kind of purposes of the p-type layer of above-mentioned preparation method preparation, this p-type layer can be used for binode and
Three junction amorphous silicon germanium thin film solar cell top batteries.
Present invention also offers a kind of double junction non-crystal silicon germanium film solar cell, it is by the lining arranging from bottom to top successively
Bottom, back electrode, bottom battery, top battery and front electrode constitute, wherein, top battery by N-shaped doped layer, amorphous silicon intrinsic absorbed layer and
P-type doped layer is constituted, and the p-type doped layer of this top battery is to be made up of above-mentioned preparation method.
Present invention also offers a kind of three junction amorphous silicon germanium thin film solar cells, it is by the lining arranging from bottom to top successively
Bottom, back electrode, bottom battery, intermediate cell, top battery and front electrode are constituted, and wherein, top battery is by N-shaped doped layer, non-crystalline silicon originally
Levy absorbed layer and p-type doped layer is constituted, wherein, the p-type doped layer of this top battery is to be made up of above-mentioned preparation method.
The operation principle of the present invention: the p layer of the middle subcell that compares and the sub- battery of bottom, using higher hydrogen dilution ratio
Example, higher power and air pressure and relatively low depositing temperature, the higher p-type nanometer silicon layer of formation of deposits band gap width, by it
It is applied to push up in battery, the high-energy photons that originally a part is absorbed by p layer can be pushed up through the higher p layer of this band gap
Battery intrinsic layer effectively absorbs generation electron hole pair, even if therefore top cell thickness is maintained at relatively low level, also can produce
The current value needing.Top cell thickness is relatively low, more light can be allowed to be incident to middle subcell and bottom battery so that following
Sub- battery produces enough electric currents, is formed " top battery current restriction effect ", this can be designed so that binode and three junction batteries
Current value reach optimum, meanwhile, the p layer of broad-band gap can also improve the open-circuit voltage of top battery further, thus improving electricity
The overall open-circuit voltage in pond.
The invention has the beneficial effects as follows: the top cell p type that this band gap width of method of the present invention preparation is higher adulterates
Layer, so that the electric current of top battery is kept low, forms top battery current restriction effect, optimizes binode and three knot electricity
The currents match in pond, improves the overall open-circuit voltage of battery simultaneously, simultaneously as the optimization between each sub- battery, the filling out of battery
Fill the factor also can rise, thus improving binode and the photoelectric transformation efficiency of three junction amorphous silicon germanium hull cells.
Specific embodiment
With reference to embodiments technical scheme is further described.
Embodiment 1
With the thick flexible polyimide of 25 mm as substrate, using plasma assistant chemical vapor deposition method (pecvd,
Operating frequency is 13.56 mhz), it is combined, having ag/zno, the binode amorphous that n-i-p structure is deposited on the substrate of back reflection layer
Germanium-silicon film (a-si:h/a-sige:h), wherein n-layer reacting gas are hydrogen, silane, phosphine, and thickness is about 50 nm；I layer is anti-
Answer gas to be hydrogen, silane and germane, thickness is about 200～300 nm；P layer reacting gas is hydrogen, silane, borine, thickness
It is about 15～30 nm.Using magnetically controlled sputter method (operating frequency is 13.56 mhz) deposition identical ito(indium tin oxide)
Thin film is about 70 nm as front electrode, thickness.
The amorphous silicon germanium thin film battery of above structure all employs V-shaped graded bandgap knot in the deposition process of intrinsic layer
Structure.Battery at 25 DEG C, am 0 solar spectrum (1353 w/m2) under carry out solar cell output characteristics test.
It is prepared for nano-silicon (nc-si:h) p-type of common non-crystalline silicon (a-si) p-type layer and different technology conditions respectively
As the p layer of double junction non-crystal silicon germanium film battery top battery, design parameter as shown in table 1, corresponds to the i-v performance such as table of battery to layer
Shown in 2.From micro-scale, each film layer of all silicon-base thin-film batteries is all nanostructured, common in order to be different from
Non-crystalline silicon and microcrystal silicon, the p layer of this broad-band gap is specially referred to as " nano-silicon " (nc-si:h) by research worker, to be different from
The p-type non-crystalline silicon of common doping.
In prior art, the p layer of typical non crystalline structure using the sedimentary condition similar to n-layer, be applied in battery by
Restriction in top cell band gap width leads to battery open circuit voltage and fill factor, curve factor all relatively low, two sub- battery (top battery, bottoms
Battery) electric current coupling poor lead to short-circuit current density very low, be rarely employed at present.Using institute in non-crystalline silicon single junction cell
The p-type layer condition being usually used, i.e. nc-si:h-1 condition in table 1, the open-circuit voltage of battery sample b and fill factor, curve factor are all significantly
Lifting, this improvement has been applied at large in prepared by the technique of silicon-based thin film solar cell.On this basis, using optimization
New nanometer p layer condition afterwards, i.e. nc-si:h-2 condition, the open-circuit voltage of double junction non-crystal silicon germanium film battery sample c of preparation and
Fill factor, curve factor improves further, and each sub- battery current coupling of optimization also makes its short-circuit current density get a promotion, so that
The cell photoelectric conversion efficiency that must prepare is further enhanced.This test result indicate that, new p-type doped layer compares
Commonly used p-type layer, is more suitably applied in the middle of the top battery of binode battery.
The top battery p layer preparation parameter of table 1 different structure
The top battery p layer corresponding double junction non-crystal silicon germanium battery performance of table 2 different structure
Embodiment 2
The p-type layer of three kinds of different preparation parameters is applied to three junction amorphous silicon germanium hull cell (a-si:h/a-sige:h/
A-sige:h, in the middle of top battery), the battery i-v characteristic of preparation is as shown in table 3.
The top battery p layer of sample d adopts common p-type layer condition, and sample e and f is respectively adopted nc-si:h-1 condition and nc-
Si:h-2 condition, can clearly find out, basically identical with the rule of double junction non-crystal silicon germanium serial experiment, with p layer condition
Update, every i-v characterisitic parameter of battery all obtains optimizing lifting.
The top battery p layer corresponding double junction non-crystal silicon germanium battery performance of table 3 different structure
Two above example illustrates, this new p-type layer after optimizing is highly suitable to be applied for binode and three knots
In the middle of the top battery of amorphous silicon germanium thin film solar cell, it can make the performance of battery be highly improved.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
Multiple modifications and substitutions all will be apparent from.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (7)
1. a kind of preparation method of amorphous silicon germanium thin film solar cell top cell p type layer is it is characterised in that the method is employing etc.
Plasma enhanced chemical vapor sedimentation, the p-type layer of deposition preparation top battery, reacting gas is hydrogen, silane, borine, preparation temperature
Within 100 DEG C, during deposition, the gas flow volume ratio of hydrogen, silane and borine is maintained at 150～200:1:3～8 to degree, its
In, borine is with diluted in hydrogen, and volumetric concentration is 0.5% borine hydrogen gas mixture；Chamber internal gas pressure is maintained at 160-220
Pa, within the chamber power density is in 300 mw/cm2More than；Described p-type layer band gap width is in 2.0 more than ev；Described p-type layer
Thickness is 15～30nm.
2. preparation method as claimed in claim 1 is it is characterised in that described preparation temperature is 70～80 DEG C.
3. preparation method as claimed in claim 1 it is characterised in that deposition when chamber internal gas pressure be maintained at 200 pa.
4. a kind of p-type layer of the preparation method preparation of employing claim 1 is it is characterised in that this p-type layer band gap width is 2.0
More than ev, thickness is 15～30nm.
5. a kind of purposes of the p-type layer of preparation method preparation using claim 1 it is characterised in that this p-type layer can be used for double
Knot and three junction amorphous silicon germanium thin film solar cell top batteries.
6. a kind of double junction non-crystal silicon germanium film solar cell, its by the substrate arranging from bottom to top successively, back electrode, bottom battery,
Top battery and front electrode are constituted, and wherein, top battery is made up of N-shaped doped layer, amorphous silicon intrinsic absorbed layer and p-type doped layer, its
It is characterised by, the p-type doped layer of this top battery is the p-type layer being made up of the preparation method of claim 1.
7. a kind of three junction amorphous silicon germanium thin film solar cells, its by the substrate arranging from bottom to top successively, back electrode, bottom battery,
Intermediate cell, top battery and front electrode are constituted, and wherein, top battery is adulterated by N-shaped doped layer, amorphous silicon intrinsic absorbed layer and p-type
Layer is constituted it is characterised in that the p-type doped layer of this top battery is the p-type layer being made up of the preparation method of claim 1.
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| CN1697201A (en) * | 2005-06-20 | 2005-11-16 | 南开大学 | P type window layer in use for solar cell of silicon thin film, and preparation method |
| CN102945886A (en) * | 2012-12-07 | 2013-02-27 | 上海空间电源研究所 | Composite layer-containing flexible substrate silicon-base multi-junction laminated solar battery |
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| CN1697201A (en) * | 2005-06-20 | 2005-11-16 | 南开大学 | P type window layer in use for solar cell of silicon thin film, and preparation method |
| CN102945886A (en) * | 2012-12-07 | 2013-02-27 | 上海空间电源研究所 | Composite layer-containing flexible substrate silicon-base multi-junction laminated solar battery |
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