CN103975448A - Method of manufacturing an intermediate reflector layer - Google Patents

Method of manufacturing an intermediate reflector layer Download PDF

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Publication number
CN103975448A
CN103975448A CN201280054240.9A CN201280054240A CN103975448A CN 103975448 A CN103975448 A CN 103975448A CN 201280054240 A CN201280054240 A CN 201280054240A CN 103975448 A CN103975448 A CN 103975448A
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layer
irl
series
sih
refractive index
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L.洛伊夫格伦
M.德斯佩斯塞
J.巴拉特
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TEL Solar AG
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Oerlikon Solar AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/076—Multiple junction or tandem solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
    • 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
    • Y02E10/52—PV systems with concentrators
    • 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

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

An intermediate reflector layer in a thin film tandem solar cell is manufactured in that there is deposited a layer by PEDVD in a process atmosphere which is fed by a gas mixture comprising H2, SiH4, a dopant gas and CO2. The flow ratio of H2 to SiH4 is selected to be between 100 and 400 and the CO2 to SiH4 flux ratio is selected as high as possible, thereby maintaining electric conductivity of the layer.

Description

The method in reflector in the middle of manufacturing
Photovoltaic devices or solar cell are the device that light is converted into electric energy.Thin-film solar cells for example, is the Si base film of 100 nm-2 μ m owing to allowing to use cheap base material (, glass) and thickness, particular importance in low cost volume production.Be PECVD method for a kind of method the most often using that deposits such Si basic unit.
Simple thin-film solar cells is usually included in transparent (glass) base material that deposits on described base material and transparent conductive oxide (TCO) layer, that is, and and the front contact (or electrode) of solar cell.Silicon base layer deposits on contacting before TCO: the first Si layer for just adulterating, that is, p-layer, follows by characteristic absorption layer (i-layer) and the negative n-layer adulterating.Three Si layers form p-i-n knot.The major part of Si layer thickness is occupied by i-layer, and photoelectric conversion mainly occurs at this place.At the top of Si layer, deposit another tco layer, also referred to as back of the body contact.Before TCO, contact layer and back contact can be made up of zinc oxide, tin oxide, ITO or other suitable material.After back of the body contact, conventionally apply white reflector, reflect back into active layer for unabsorbed light also.
Fig. 1 shows series connection-knot silicon film solar batteries known in the art.Such thin-film solar cells 50 generally includes first or front electrode 42, and two or more have semiconductive thin film p-i-n knot 51 and 43 of corresponding layer 52-54 and 44-46, and second or back electrode 47, they are sequence stack on base material 41.Each p-i-n knot 51,43 or film photoelectric conversion unit comprise the i type layer 53,45 being clipped between p-type layer 52,44 and N-shaped layer 54,46 (p-type=just adulterating, N-shaped=negative doping).In the present context, " characteristic substantially " is interpreted as unadulterated or presents and there is no the doping obtaining.Photoelectric conversion mainly occurs in this i type layer; Therefore also referred to as absorbed layer.
Depend on i type layer 53,45 crystalline fraction (degree of crystallinity), the p-i-n knot of solar cell or photoelectricity (conversion) device is characterized as amorphous (a-Si, 53) or crystallite (μ c-Si, 45) solar energy p-i-n knot, irrelevant with the degree of crystallinity kind of adjacent p-layer and n-layer.As general in this area, microcrystalline coating is interpreted as comprising the layer of the silicon metal (so-called crystallite) of remarkable mark in amorphous matrix.Stacking series connection or the triple junction photovoltaic cell of being called of p-i-n knot.The combination (as shown in Figure 1) of amorphous and crystallite p-i-n-knot is also referred to as amorphous/crystallite (micromorph) series-connected cell.
The present invention relates to a kind of photovoltaic devices of the stacking multiple knot that comprises mentioned kind.It is not limited to the tandem junction battery with two stacking p-i-n knots, but can be usefully for the multiple joint solar cell of numerous species, in this specification and claim by these all be all called " series-connected solar cells ".
Known in the art, by substantially arranging one or more selective reflecting layers between knot, can strengthen the efficiency of the stacking p-i-n knot of setting forth kind herein.Fig. 1 in reference can carry out in the interface of layer 53/54 and/or 54/44 and/or 44/45 and/or even this point in 45/46.IRL, also referred to as middle reflector, is abbreviated as in such intermediate layer.
US 5,021,100 has described a kind of multiple cell photovoltaic device, and it comprises the first and second solar energy p-i-n knot and conduction or dielectric selective reflection films between them that are connected in series.Select the thickness of this selective reflection film with reflection short-wavelength light and transmission long wavelength light, short-wavelength light can absorb by the first solar energy p-i-n knot (top junction 51), and long wavelength light is not absorbed or less absorption by top p-i-n knot, but can preferably absorb by bottom p-i-n knot.Selective reflection film can comprise ZnO, TiO, SnO 2, ITO (being conductibility), SiO 2, SiN, TaO, SiC (being dielectricity).
In the present invention, describe the various improvement to existing IRL and their manufacture method, their capable of being combined or uses separately, with further propulsive efficiency, improve optics and/or the electric property of the thin-film solar cells of described kind.
Realize this point by a kind of method of manufacturing middle reflector IRL in film series-connected solar cells, described method is included in by H 2: SiH 4flow-rate ratio is the H that comprises of 100-400 2, SiH 4, dopant gas and CO 2the deposition process atmosphere of admixture of gas feed in, by PEDVD sedimentary deposit, and by by CO 2: SiH 4flow-rate ratio is chosen as high as far as possible, thereby keeps the conductivity of described layer.
Further realize the object of elaboration by series-connected solar cells, described power brick is containing at least one the IRL layer being substantially made up of the more rich region of different SiO and the different purer regions of SiO, in the direction substantially vertical with the surface of described layer existence thereon, form the nanostructure of the wire harness with elongation.The structure of IRL layer material can be thus by electron energy loss spectroscopic methodology and energy filtering transmission electron microscopy (EFTEM) research, for example, by G.Nicotra, Appl.Surf. Sci 205 (2003) or S.Schamm, known to Ultramicroscopy 108 (2008).
Illustrate the present invention by accompanying drawing by good embodiment of the present invention now.
Accompanying drawing shows:
Fig. 1 illustrates prior art tandem thin-film Silicon photrouics.
Fig. 2 is that refractive index is to the H applying in VHF PECVD deposition process for middle reflector according to the present invention 2/ SiH 4the dependence of flux ratio.
Fig. 3 is with corresponding H 2/ SiH 4the nanostructure of three kinds of IRL materials and the result of electron energy loss spectroscopic methodology/energy filtering transmission electron microscopy of flux ratio deposition.
Fig. 4 is the nanostructure of the IRL material of the present invention that deposits on coarse ZnO surface profile.
Fig. 5 deposits the deposition rate of IRL material layer to H 2/ SiH 4the dependence of flux ratio.
Fig. 6 is the refractive index of the IRL layer material dependence to the oxygen content in material.
Fig. 7 illustrates an embodiment of series-connected cell of the present invention.
Fig. 8 is according to the characteristic of the series-connected cell of the embodiment of Fig. 7.
Fig. 9 is for according to Fig. 7 but there is no invention and IRL layer is provided and has the degradation characteristic of the series-connected cell of IRL layer according to the present invention.
Figure 10 be processing atmosphere under the Ar of difference amount, the dependence of refractive index to deposition process pressure.
Figure 11 is that the refractive index of IRL layer material is to being applied to the CO of deposition process atmosphere 2/ SiH 4the dependence of flux ratio.
Figure 12 is the refractive index of the IRL material dependence to the deposition rate for depositing described material.
Figure 13 is battery current I sCto use the impurity gas of different amounts and the dependence of Ar in deposition process atmosphere.
Figure 14 is the difference processing depending on according to Figure 13, the battery efficiency obtaining.
Figure 15 is the difference processing that still depends on Figure 13 and 14, the initial cell voltage V with degrading oC.
Figure 16 is the difference processing that still depends on elaboration, the initial film factor with degrading.
Figure 17 is the processing that still depends on elaboration, the initial battery current I with degrading sC.
Figure 18 is the processing that still depends on elaboration, the initial efficiency with degrading.
Figure 19 and 20 is for using the characteristic of setting forth the initial and degraded of the series-connected cell of manufacturing through the IRL layer of difference processing according to Figure 13-18.
Figure 21 is the dependence of the refractive index of the IRL layer material amount to the Ar existing in layer deposition process atmosphere.
Figure 22 is the dependence of the amount of deposition rate to the argon in inflow IRL layer deposition process atmosphere.
Figure 23 is that oxygen content in IRL layer material and refractive index are respectively to entering the dependence of Ar flow of processing atmosphere.
Figure 24 is that deposition rate and refractive index are to SiH 4the dependence of flow.
Can be recognized by method of the present invention and series-connected cell of the present invention, the major part of IRL material is made up of silica.Therefore, below by IRL of the present invention also referred to as SOIR, reflector in the middle of silica.
On the one hand, SOIR must meet the requirement of low-refraction, on the other hand, must meet the requirement that high transverse electric is led.And in the time that the O content in material is high, the refractive index of SOIR material is low, in the time that the O content in material is low, realizes high transverse electric and lead.
In Fig. 2, show to be the light of 600 nm for wavelength, the impact of hydrogen dilution factor refractive index.In addition, show that refractive index is to H 2/ SiH 4dependent three characteristics of flux ratio, parameters C O 2/ SiH 4flux ratio improves in the direction of arrow.In addition, show that in the figure SOIR-layer material becomes the demarcation of blocking-up battery from conductibility.
The visible H that works as 2/ SiH 4when flux ratio improves, about when SOIR-layer material becomes the disconnected demarcation characteristic of resistance towards lower refractive index shift.Therefore, in the example according to Fig. 2, as seen when selecting the CO of relative high flux ratio 2/ SiH 4time, on the one hand, with in the H that exceedes 250 2/ SiH 4flux ratio, reaches the low-refraction just over 1.8, and SOIR-layer material still conducts.
Derive from SOIR layer material deposition according to the example of Fig. 2, it uses PECVD (especially VHF PECVD), to feed SiH in deposition process atmosphere 4, H 2, CO 2, and utilize PH 3as impurity gas.Therefore, people can say in processing and deposit SOIR-layer by PECVD in atmosphere, and this processing atmosphere is by H 2: SiH 4flow-rate ratio is the H that comprises of 100-400 2, SiH 4, dopant gas and CO 2admixture of gas feed, thereby by CO 2: SiH 4flux ratio is chosen as high as far as possible, thereby keeps the conductivity of the layer obtaining.As seen in Figure 2, at different H 2/ SiH 4under flux ratio, realize similar refractive index, but whether SOIR-material keeps conductivity finally to pass through CO 2/ SiH 4flux ratio control.Therefore advantageously utilizing two independently variablees, is H on the one hand 2/ SiH 4flux ratio is CO on the other hand 2/ SiH 4flux ratio, there are two requirements the to realize SOIR material of (be on the one hand, low-refraction and be high transverse conduction on the other hand).
Recognize, the nanostructure of obvious obtained SOIR-layer material is crucial.
In Fig. 3, show and use different H 2/ SiH 4the nanostructure of three kinds of SOIR-layer materials that dilution factor is realized.The material of the left-hand side of mark " blocking-up " shows not structurized SiO substantially xmaterial.This is in 3 low dilution factor H 2/ SiH 4.
Under 100 dilution factor, according to diagram in the middle of mark " line of demarcation ", can identify SiO xmore rich black region and the with it different purer region (white portion) of SiO.Exist in the direction of surperficial perpendicular thereon with described layer, the structure of long thin wire harness starts to identify.In deposition growing direction, the average length in the more rich wire harness of SiO region is at least in 5 nm-10 nm scopes.This SOIR-layer material has presented conductivity.
According to Fig. 2, the dexter material of mark " conductibility " is based upon on 300 dilution factor.Wherein be greater than 20 nm in the average length of the direction of growth in the more rich wire harness of SiO region, and in vertical with it direction, their average length is less than 10 nm.
This material presents the good conductive with low-refraction combination.
Further deposit on coarse ZnO surface according to the layer material of " conductibility " layer material result of Fig. 3, form taper thing, as shown in Figure 4.μ c-Si is placed between ZnO and SOIR material.Clearly establish, the nanostructure of preserving SOIR material on rough surface, the average peak of peak roughness is at least 200 nm.
This has significantly expanded the possible range of application of such SOIR-layer.
For reflector IRL (thereby being SOIR of the present invention) in the middle of manufacturing, another machined parameters that must think over is deposition rate, is especially conceived to industry manufacture.
Fig. 3 demonstration, (referring to Fig. 2) on the one hand, at H 2/ SiH 4flux ratio is 100 times, and refractive index is in the upper limit, and conductivity is at lower limit.And at H 2/ SiH 4flux ratio is 300 times, and refractive index and conductibility are all improved, and Fig. 5 shows when improving H 2/ SiH 4flux ratio time, growth rate reduce.Therefore,, in the good embodiment of the inventive method, select H 2: SiH 4flux ratio is at least about 300, under this value, according to Fig. 5, still causes the approximately acceptable deposition rate of 0.6/s.
By suitable adjusting deposition process, thus fine adjustment CO 2: SiH 4the amount of flux ratio and dopant gas, can further improve extremely approximately 3.5/s of deposition rate, for the light of 600 nm wavelength, the refractive index obtaining is 1.66, and keep the thin wire harness nanostructure of the length of SOIR-material, substantially according to dexter diagram in Fig. 3.Thereby, find to realize this further optimization of setting forth, comprise the total oxygen content of considering in layer material.
As Fig. 6 shows, under the total oxygen content improving in layer material, refractive index reduces towards the low value of high expectations.Fig. 6 shows another good embodiment of the inventive method, comprises the total content of oxygen in layer material is maximized, and is preferably 39%-52%, preferably at least 50%.Under such oxygen content, for the light of 600 nm wavelength, it is significantly low that refractive index becomes, as expected.
Fig. 7 shows good embodiment, and IRL (according to the present invention, being SOIR) is wherein provided.According to Fig. 7, series-connected solar cells comprises a-Si and μ c-Si p-i-n knot 51a and 43a.As shown, at least one in front electrode layer 47a and dorsum electrode layer 42a is ZnO, and according in the specific embodiments of Fig. 7, two electrode layers are ZnO.As base material, preferably use glass baseplate 41a.A-Si top p-i-n knot 51a is present on front electrode 42a.
IRL-layer 60 (according to the present invention, thinking SOIR-layer) extends as n doped layer deposition and in a part of thickness length of the n doped layer 54a of top a-Si p-i-n knot 51a.Thereby as shown in the good embodiment of Fig. 7, the IRL-layer 60 of elaboration embeds in n-layer 54a.
As seen from Figure 7, in the good embodiment of manufacture series-connected cell of the present invention, the latter comprises a-Si and μ c-Si p-i-n knot 51a and 43a.Thereby in good embodiment, in front electrode layer and dorsum electrode layer, at least one is deposited by ZnO.Thereby in good embodiment, it is upper that front electrode is present in glass baseplate 41a, is then a-Si p-i-n top junction 51a.IRL layer 60, as n doped layer deposition, extends in a part of thickness length of the n layer 54a tying at a-Si p-i-n.In good embodiment, IRL layer 60 embeds the n-layer of a-Si p-i-n knot.
As seen from Figure 7, the good embodiment of series-connected cell of the present invention comprises a-Si and μ c-Si p-i-n knot, front electrode layer and dorsum electrode layer.Thereby in good embodiment, at least one in front electrode layer and dorsum electrode layer is essentially ZnO.In good embodiment, front electrode is present on glass baseplate.In good embodiment, a-Si p-i-n top junction is present on front electrode layer.In good embodiment, IRL layer is n doped layer, and it extends in a part of thickness length of the n layer of a-Si p-i-n knot, and in another good embodiment, embeds the n-layer of a-Si p-i-n knot.
In the series-connected solar cells with structure as shown in Figure 7, provide IRL, more specifically, SOIR-layer 60.The layer of setting forth is with the deposition rate deposition of 3.5/s.Although keep the nanostructure of SOIR material, realize the low-refraction at least about 1.7.The thickness of SOIR-layer 60 is 60 nm.
Fig. 8 shows the characteristic that series-connected solar cells obtains, and the characteristic that wherein (a) sets forth is the characteristic containing the comparison series-connected cell of IRL-layer 60 according to Fig. 7 but not.Characteristic (b) characteristic that the series-connected cell of the elaboration with IRL-layer 60 obtains of serving as reasons.About the thickness of SOIR layer, test and show, in good embodiment, thickness is 40-90 nm, thus in improved embodiment, thickness is 60-80 nm.Significantly, target is minimum thickness, for example, and aspect manufacturing in industry.Therefore the inventive method good embodiment derives from IRL (SOIR) layer that deposit thickness is 40 nm-90 nm (further improving 60 nm-80 nm).
Apparent with respect to the improvement that does not contain the series-connected cell of Fig. 7 of IRL for professional and technical personnel:
V oc, form factor (form factor) FF and battery current I sCall be improved.
Starting efficiency is 12.8%, stablizes to 11.2% through 1000 hours Sunlight exposures.Therefore,, for high deposition rate, also realize good stability.
Fig. 9 shows the battery behavior of following series-connected cell: according to Fig. 7 but not containing the series-connected cell of IRL-layer, and have according to the present invention IRL-layer 60 according to the series-connected cell of Fig. 7, and according to Fig. 8.In Fig. 9, characteristic (a1) is set forth the initial characteristic that does not contain the series-connected cell of IRL, (a2) set forth the characteristic after 1000 hours Sunlight exposures containing the series-connected cell of IRL, characteristic (b1) is set forth the initial characteristic of series-connected cell of the present invention (therefore having IRL), and characteristic (b2) is set forth the characteristic of series-connected cell of the present invention (therefore having IRL) after 1000 hours Sunlight exposures.
Some piths of finding up to now:
● the nanostructure of the IRL material of as above setting forth is crucial for the good electrical properties of obtained series-connected cell.
● under low-refraction, realize high top battery electric current (, 14.3mA/cm 2), IRL-layer deposits on rough surface as the LPCVD ZnO of growth.
Even ● under the high deposition rate up to 3.5/s, realize nanostructure and be reduced to or even lower than 1.7 refractive index.
● the series-connected cell obtaining shows without V oClight degradation and 11.2% stable efficiency.
Show that good SOIR of the present invention (reflector in the middle of silica) comprises SiO xlayer, its refractive index is 1.7-1.9, and thickness is 40-90 nm, preferably 60-80 nm.Oxygen content is 39-52%, can realize even more such refractive index of low value, as shown.
In good embodiment, IRL layer is arranged as a part for (embedding) n-layer 54, is therefore adulterated to strengthen conductibility.
In another good embodiment, IRM layer can deposit in the processing atmosphere that contains Ar.As indicated, add SiH 4, CO 2and dopant gas, to realize degree of crystallinity and conductibility.
To add argon gas to allow the refractive index n of IRL towards lower value skew, as shown in figure 10 for the deposition gases of IRL deposition.
As seen from Figure 10, in processing atmosphere, add Ar to reduce refractive index, in the time that tonnage improves, it is more remarkable that this point becomes.Can reach the refractive index lower than 1.7, for example, use the tonnage of 4 millibars.
Processing conditions/flux (sccm) is:
H 2：1500
SiH 4：15
PH 3(0.1%)：500
CO 2：25
CO 2/ SiH 4=1.67 (flux ratios)
Power: ~ 850 W
Add 100sccm Ar to cause refractive index to be significantly offset to 1.7 and even lower than 1.7 to above-mentioned formula.
For n doping, by the dopant that correspondingly feeds intake, especially PH 3, can advance the conductibility of IRL layer material.Thereby Figure 11 shows the refractive index of IRL layer material and depends on CO 2/ SiH 4the development of flux ratio does not wherein add Ar in processing atmosphere.In Figure 11 effectively:
Point to the triangle of left-hand side: 50 sccm PH 3(2%) equal 1.0 sccm PH 3
Point to dexter triangle: 100 sccm PH 3(2%) equal 2.0 sccm PH 3
Mark=blocking-up battery of filling.
Processing conditions/flux (sccm):
H 2: 1500 (maximum 1950)
SiH 4：15
(PH 3(0.1%)：500)
Power: ~ 850 W
Pressure: 4 millibars
Figure 12 shows the impact of the refractive index of deposition rate on IRL layer material.Notice, under the deposition rate scope of 3.3/s-3.8/s, reach lowest refractive index, be low to moderate approximately 1.7.
In following examples, research is at the CO of 32 sccm 2under flux, Ar and PH 3(2%) impact on amorphous/crystallite series-connected cell.
1) battery parameterfor:
4.5μm ZnO
250 nm a-Si:H top battery
Reflector (SOIR) in the middle of 60 nm silica
1.8μm μc-Si:H
Machined parameters is:
Figure 13 and Figure 14 show result.For result (a), under the deposition rate of 3.4/s, the refractive index that realizes IRL layer material is 1.66.
2) battery parameter is:
AR glass
The thick ZnO of 2 μ m
280 nm a-Si:H
The thick SOIR of 60 nm or the thick SOIR of 80 nm, be named as system B
2.4 μm μc-Si:H
The machined parameters of SOIR is:
The results are shown in Figure 15,16,17 and 18.
The initial characteristic obtaining of amorphous/crystallite series-connected cell is shown in Figure 19, and the characteristic after light degradation is shown in Figure 20:
Characteristic (a): do not apply SIOR, SOIR thickness 60 nm
Characteristic (b): the PH as mentioned above with 50 sccm 32% machined parameters, SOIR thickness 60 nm
Characteristic (c): there are as mentioned above 100 sccm PH 32% and 100 sccm Ar flux, SOIR thickness 60 nm
Characteristic (d): SOIR thickness 80 nm.
Difference to IRL is further studied, and whether described difference depends on as established to H 2, SiH 4, CO 2, PH 3in mixture, add Ar or H 2thereby replaced and cause H by Ar part 2the constant flow rate of+Ar.
A) flow increasing:
Flux (sccm):
H 2：1900
SiH 4：15
PH 3(2%)：100
CO 2：32
CO 2/SiH 4：2.13
Ar：0-290
Power: approximately 850 W
B) constant flow rate:
Flux (sccm):
H 2+Ar：1900
SiH 4：15
PH 3(2%)：100
CO 2：32
CO 2/SiH 4：2.13
Ar：0-290
Power: approximately 850 W
The results are shown in Figure 21.
Please note that n value does not reach 1.56.Thereby the Ar amount improving in the deposition process atmosphere for SOIR layer reduces deposition rate.
Figure 22 shows according to B) this reduction of constant flow rate processing.
For the SOIR deposition process B setting forth), the oxygen content in Figure 23 display layer material and the dependence of the refractive index of layer material to Ar flow.In Figure 23, measurement point (a) is set forth oxygen content, and the point of mark (b) is set forth refractive index.
Please not consistent with Fig. 6:
The measurement of nanostructure is shown
Under 52% O concentration, n=1.71
Under 48% O concentration, n=1.82
Under 39% O concentration, n=1.88.
Because under constant flow rate processing, Ar replaces H 2, H 2/ SiH 4flux ratio reduce because Fig. 5 is presented at the H of reduction 2/ SiH 4under flux ratio, deposition rate improves, and along with the Ar flux improving, constant flow rate processing should cause the deposition rate improving.
Use following machined parameters, the refractive index of research deposition rate and IRL material is to SiH 4the dependence of flux.The results are shown in Figure 24.Point (a) is set forth the measurement point of deposition rate, and point (b) is set forth refractive index.
Note that at constant H 2the SiH improving under flux 4flux causes the H reducing 2/ SiH 4flux ratio.Therefore consistent with prior art result (referring to Fig. 2), at sufficiently high SiH 4under flux, IRL material becomes has very much resistive (referring to full measurement point).It should be understood that refractive index keeps substantially stable, is not subject to SiH 4the impact of variations of flux.
Machined parameters:
Flux (sccm):
H 2：1500
PH 3(2%)：50
CO 2：32-64
CO 2/SiH 4：2.1
Power: 850W
We find other pith of our research:
For amorphous/crystallite series-connected cell, two-forty SOIR (~ 3.5/s) work is good: there is no current loss, and in the similar optical delta of low rate SOIR, do not have or very little other degraded.
Approximately the deposition rate of 4/s (for thin SOIR 50-60 nm) should be possible, has good performance.
This formula is used in the n-SiO at amorphous/crystallite battery back x.Can increase thick transparent layer to battery performance.

Claims (18)

1. a method of reflector IRL in the middle of manufacturing in film series-connected solar cells, described method comprises: by H 2: SiH 4flow-rate ratio is the H that comprises of 100-400 2, SiH 4, dopant gas and CO 2the processing atmosphere of admixture of gas feed in, by PEDVD sedimentary deposit, and by by CO 2: SiH 4flux ratio is chosen as high as far as possible, thereby keeps the conductivity of described layer.
2. the method for claim 1, thus to feed PH in described processing atmosphere 3as dopant gas.
3. the method for claim 1 or 2, described method comprises selects described H 2: SiH 4flux ratio is at least about 300.
4. the method for any one in claim 1-3, makes the total content of oxygen in described layer maximize thus, is preferably 39%-52%, and preferably at least 50%.
5. the method for any one in claim 1-4, wherein said series-connected solar cells comprises a-Si and μ c-Si p-i-n knot, preferably, in electrode layer and dorsum electrode layer, at least one is deposited by ZnO, and wherein preferably described front electrode is present on glass baseplate, then be a-Si p-i-n top junction, described IRL layer, as n doped layer deposition, extends in a part of thickness length of the n layer of tying at described a-Si p-i-n, preferably embeds the described n-layer of described a-Si p-i-n knot.
6. the method for claim 5, described method comprises that deposit thickness is 40 nm-90 nm, the preferably described IRL layer of 60 nm-80 nm.
7. the method for any one in claim 1-6, described method comprises in described processing atmosphere and adds Ar.
8. the method for claim 7, described method comprises by tonnage, and the refractive index of the material of described IRL layer is minimized.
9. the method for any one in claim 1-8, described method comprises by adjusting and produces PH 3the n-dopant of flux, advances the conductivity of the material of described IRL layer.
10. a series-connected solar cells, described power brick is containing at least one the IRL layer being substantially made up of the more rich Si base region of different SiO and the purer Si base region of SiO, in the direction substantially vertical with the surface of described layer existence thereon, form the nanostructure of the wire harness with elongation.
The series-connected solar cells of 11. claims 10, the described wire harness in the more rich region of described SiO in the average length of described direction at least within the scope of 5 nm-10 nm.
The series-connected cell of 12. claims 2, wherein said average length is greater than 20 nm.
The series-connected cell of any one in 13. claim 10-12, wherein said IRL layer deposits on rough surface, and the average peak of its peak roughness is at least 200 nm.
The series-connected cell of any one in 14. claim 10-13, the oxygen content of the material of described IRL layer is 39%-52%, preferably at least 50%.
The series-connected cell of any one in 15. claim 10-14, described power brick is containing a-Si and μ c-Si p-i-n knot, wherein at least one is preferably made up of ZnO substantially for front electrode layer and dorsum electrode layer, preferably described front electrode is present on glass baseplate, a-Si p-i-n surplus is on described front electrode layer, described IRL layer is n doped layer, in a part of thickness length of the n layer of tying at described a-Si p-i-n, extends, and preferably embeds the described n-layer of described a-Si p-i-n knot.
The series-connected cell of any one in 16. claim 10-15, the thickness of wherein said IRL layer is 40-90 nm, preferably 60-80 nm.
The series-connected cell of any one in 17. claim 10-16, is wherein the light of 600 nm for wavelength, and the refractive index of the material of described IRL layer is not more than 1.7-1.9.
The series-connected cell of 18. claims 17, is wherein the light of 600 nm for wavelength, and the refractive index of the material of described IRL layer is lower than 1.7.
CN201280054240.9A 2011-09-06 2012-09-04 Method of manufacturing an intermediate reflector layer Pending CN103975448A (en)

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