CN114156371A - Silicon-based FeSi2Thin film quantum well solar cell and preparation method thereof - Google Patents
Silicon-based FeSi2Thin film quantum well solar cell and preparation method thereof Download PDFInfo
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- CN114156371A CN114156371A CN202111221046.2A CN202111221046A CN114156371A CN 114156371 A CN114156371 A CN 114156371A CN 202111221046 A CN202111221046 A CN 202111221046A CN 114156371 A CN114156371 A CN 114156371A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 53
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000010409 thin film Substances 0.000 claims abstract description 219
- 229910005331 FeSi2 Inorganic materials 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 71
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 63
- 238000000137 annealing Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 71
- 229910005347 FeSi Inorganic materials 0.000 claims description 49
- 238000002294 plasma sputter deposition Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 229910005329 FeSi 2 Inorganic materials 0.000 claims 26
- 239000002131 composite material Substances 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 229910021419 crystalline silicon Inorganic materials 0.000 description 19
- 239000010408 film Substances 0.000 description 14
- 239000013077 target material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000031700 light absorption Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910006578 β-FeSi2 Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910006542 α-FeSi Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/10—Semiconductor bodies
- H10F77/14—Shape of semiconductor bodies; Shapes, relative sizes or dispositions of semiconductor regions within semiconductor bodies
- H10F77/146—Superlattices; Multiple quantum well structures
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- H10F19/30—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells
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Abstract
The invention discloses a silicon-based FeSi2The preparation method of the thin film quantum well solar cell comprises the following steps: s1, cleaning and texturing the monocrystalline silicon substrate; s2, preparation of n-type FeSi2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A first intermediate of the thin film layer structure; s3, annealing the first intermediate; s4, preparing a second intermediate; s5, preparing a transparent conducting layer and an electrode layer on the surface of the second intermediate to obtainAnd (5) obtaining a finished product. Correspondingly, the invention also provides the prepared silicon-based FeSi2Thin film quantum well solar cells. The silicon-based FeSi2The thin film quantum well solar cell can expand the wavelength range of the absorbable incident light, improves the absorption utilization rate of the incident light, and improves the photoelectric conversion capability under weak light.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a silicon-based FeSi2A thin film quantum well solar cell and a method for manufacturing the same.
Background
The existing crystalline silicon solar cell is generally prepared by P-type crystalline silicon through phosphorus diffusion, or N-type crystalline silicon through boron diffusion, or a mode of depositing and doping an amorphous silicon film on the basis of a silicon substrate to prepare a PN junction, the existing crystalline silicon solar cell preparation mode is basically based on crystalline silicon or an amorphous silicon material, the performance limit of the prepared solar cell is limited by the electrical and optical properties of the silicon material, and the crystalline silicon cell can only absorb incident light with the wavelength of more than 1100 nm. Because the forbidden band width of the silicon material is about 1.12eV, the crystalline silicon and the amorphous silicon material basically have no absorption to long-wave band light, particularly infrared band light with the wavelength of more than 1100nm, so that the utilization rate of sunlight is low, and the photoelectric conversion efficiency is low due to the rapid reduction of the visible light ratio under the condition of weak light; therefore, new solar cell materials and structural designs need to be developed to improve the utilization rate of sunlight and simultaneously improve the photoelectric conversion efficiency under the condition of weak light.
Disclosure of Invention
The invention aims to solve the technical problem of providing a silicon-based FeSi2The preparation method of the thin-film quantum well solar cell can be used for improving production on the basis of the existing crystalline silicon solar cell production line, and has the advantages of low cost, simple process and good compatibility.
The technical problem to be solved by the invention is to provide a silicon-based FeSi2The thin film quantum well solar cell can expand the wavelength range of absorbable incident light, improves the absorption utilization rate of the incident light, and can improve the photoelectric conversion capability under weak light.
In order to solve the technical problem, the invention provides silicon-based FeSi2The preparation method of the thin film quantum well solar cell comprises the following steps:
s1, cleaning and texturing the monocrystalline silicon substrate;
s2, preparing n-type FeSi on the front side of the monocrystalline silicon substrate2A thin film layer on the back of the single crystal silicon substrate to prepare p-type FeSi2Thin film layer to obtain FeSi with n-type2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A first intermediate of the thin film layer structure;
s3, annealing the first intermediate;
s4, n-type FeSi in the first intermediate2Preparing an n-type amorphous silicon thin film layer on the surface of the thin film layer, and preparing p-type FeSi of the first intermediate2Preparing a p-type amorphous silicon thin film layer on the back surface of the thin film layer to obtain the n-type amorphous silicon thin film layer/n-type FeSi2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A second intermediate of the thin film layer/p-type amorphous silicon thin film layer structure;
s5, preparing a first transparent conductive layer on the surface of the n-type amorphous silicon thin film layer of the second intermediate, and preparing a second transparent conductive layer on the surface of the p-type amorphous silicon thin film layer of the second intermediate;
and then preparing a front electrode layer on the surface of the first transparent conducting layer, and preparing a back electrode layer on the surface of the second transparent conducting layer to obtain a finished product.
Preferably, in step S2, the n-type FeSi is prepared by plasma sputtering2Thin film layer and p-type FeSi2A thin film layer;
the n-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is (1-2): (1-4): (7-8);
the p-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is (1-2): (1-4): (5-6).
Preferably, in step S2, the background vacuum pressure of the plasma sputtering system is 5 × 10 before the plasma sputtering preparation-6～10×10-6mbar。
Preferably, in step S2, the reaction pressure of the plasma sputtering system is 1 × 10 during the plasma sputtering preparation process-3～8×10-3mbar; the flow rate of Ar gas is 100-400 sccm; the plasma generating power is 1000-2000 w; the sputtering power is 200-500 w; the applied voltage of the target material is 100-300 v; the heating temperature of the substrate is 100-400 ℃.
Preferably, in step S3, the annealing temperature is 500 to 800 ℃, and the annealing time is 30 to 90S.
Preferably, the monocrystalline silicon substrate layer is a p-type monocrystalline silicon substrate or an n-type monocrystalline silicon substrate.
Preferably, the thickness of the monocrystalline silicon substrate layer is 100-190 μm;
the n-type FeSi2The thickness of the thin film layer is 30-200 nm;
the thickness of the n-type amorphous silicon thin film layer is 5-20 nm;
the p-type FeSi2The thickness of the thin film layer is 30-200 nm;
the thickness of the p-type amorphous silicon thin film layer is 5-20 nm.
Preferably, the n-type FeSi2The doping concentration of the thin film layer is 2 multiplied by 1018～3×1018cm-3。
Preferably, the p-type FeSi2Doping concentration of thin film layerIs 2 x 1017～3×1017cm-3。
The invention also provides the silicon-based FeSi prepared by the preparation method2A thin film quantum well solar cell;
the FeSi2The thin film quantum well solar cell is sequentially provided with a front electrode layer, a first transparent conducting layer, an n-type amorphous silicon thin film layer and an n-type FeSi layer from top to bottom2Thin film layer, monocrystalline silicon substrate layer and p-type FeSi2The thin film layer, the p-type amorphous silicon thin film layer, the second transparent conducting layer and the back electrode layer.
The implementation of the invention has the following beneficial effects:
the preparation method provided by the invention can be used for improving the production on the basis of the existing crystalline silicon solar cell production line, and has the advantages of low cost, simple process and good compatibility. Prepared silicon-based FeSi2The thin film quantum well solar cell is a solar cell with' crystalline silicon/FeSi2In the prior art, most of crystalline silicon cells can only absorb incident light with the wavelength of about 1100nm, but the silicon-based FeSi solar cell provided by the invention2The thin-film quantum well solar cell can greatly expand the absorbable incident light wavelength, can absorb the incident light with the wavelength of about 1500nm, obviously improves the absorption utilization rate of the incident light, and simultaneously improves the photoelectric conversion capability under weak light.
Drawings
FIG. 1 is a silicon-based FeSi of the present invention2The structure of the thin film quantum well solar cell is schematically shown.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It is only noted that the invention is intended to be limited to the specific forms set forth herein, including any reference to the drawings, as well as any other specific forms of embodiments of the invention.
The invention provides a silicon-based FeSi2The preparation method of the thin-film quantum well solar cell is characterized in that the silicon-based FeSi2The structure of the thin film quantum well solar cell is shown in fig. 1, and comprises the following steps:
s1, cleaning and texturing the monocrystalline silicon substrate;
s2, preparing n-type FeSi on the front side of the monocrystalline silicon substrate2A thin film layer 4, preparing p-type FeSi on the back of the monocrystalline silicon substrate2A thin film layer 6 to obtain n-type FeSi2Thin film layer 4/monocrystalline silicon substrate layer 5/p type FeSi2A first intermediate of the thin film layer 6 structure;
s3, annealing the first intermediate;
s4, n-type FeSi in the first intermediate2Preparing an n-type amorphous silicon thin film layer 3 on the surface of the thin film layer 4, and preparing p-type FeSi of the first intermediate2Preparing a p-type amorphous silicon thin film layer 7 on the back surface of the thin film layer 6 to obtain the n-type amorphous silicon thin film layer 3/n-type FeSi2Thin film layer 4/monocrystalline silicon substrate layer 5/p type FeSi2A second intermediate body with a structure of a thin film layer 6/p-type amorphous silicon thin film layer 7;
s5, preparing a first transparent conductive layer 2 on the surface of the n-type amorphous silicon thin film layer 3 of the second intermediate, and preparing a second transparent conductive layer 8 on the surface of the p-type amorphous silicon thin film layer 7 of the second intermediate;
and then preparing a front electrode layer 1 on the surface of the first transparent conducting layer 2, and preparing a back electrode layer 9 on the surface of the second transparent conducting layer 8 to obtain a finished product.
The preparation method provided by the invention can be used for improving the production on the basis of the existing crystalline silicon solar cell production line, and has the advantages of low cost, simple process and good compatibility. Prepared silicon-based FeSi2The thin film quantum well solar cell is a solar cell with' crystalline silicon/FeSi2In the prior art, most of crystalline silicon cells can only absorb incident light with the wavelength of about 1100nm, but the silicon-based FeSi solar cell provided by the invention2The thin-film quantum well solar cell can greatly expand the absorbable incident light wavelength, can absorb the incident light with the wavelength of about 1500nm, obviously improves the absorption utilization rate of the incident light, and simultaneously improves the photoelectric conversion capability under weak light.
Next, each step of the preparation method will be described in detail as follows.
In step S1, a monocrystalline silicon substrate is cleaned and textured, and preferably, the monocrystalline silicon substrate is sequentially placed in an acetone solution, an ethanol solution, and deionized water, cleaned, placed in an HF solution for oscillation, rinsed with deionized water, and dried for standby.
In step S2, the n-type FeSi is preferably prepared by plasma sputtering2Thin film layer 4 and p-type FeSi2A film layer 6.
Preferably, a Fe, Si and Ni combined target material is adopted to provide raw materials for plasma sputtering, and preferably, the n-type FeSi2The thin film layer 4 adopts a Fe, Si and Ni combined target material to provide raw materials, wherein the ratio of Fe: si: the ratio of Ni is (1-2): (1-4): (7-8); the p-type FeSi2The thin film layer 6 adopts a Fe, Si and Ni combined target material to provide raw materials, wherein the ratio of Fe: si: the ratio of Ni is (1-2): (1-4): (5-6).
Prior to plasma sputtering preparation, the background vacuum pressure of the plasma sputtering system is preferably 5X 10-6～10×10-6mbar. More preferably, the background vacuum pressure of the plasma sputtering system is 8 x 10-6mbar。
In the plasma sputtering preparation process, the reaction pressure of the plasma sputtering system is preferably 1 × 10-3～8×10-3mbar; more preferably, the reaction pressure of the plasma sputtering system is 5 x 10-3mbar。
Preferably, the flow rate of the Ar gas is 100-400 sccm; more preferably, the flow rate of the Ar gas is 200 sccm.
Preferably, the plasma generating power is 1000-2000 w; more preferably, the plasma generation power is 1500 w.
Preferably, the sputtering power is 200-500 w; more preferably, the sputtering power is 300 w.
Preferably, the target application voltage is 100-300 v; more preferably, the target application voltage is 200 v.
Preferably, the substrate heating temperature is 100 to 400 ℃. More preferably, the substrate heating temperature is 200 ℃.
The plasma sputtering preparation process will affect the finally obtained FeSi2The uniform effect of the thin film layer and the particle size of the deposition can obtain FeSi with uniform particle size under the plasma sputtering preparation process condition2The thin film layer and the solar cell finally obtained have high light absorption efficiency.
In addition, in the present invention, FeSi is treated2Doping a thin film layer, preferably FeSi connected with the n-type amorphous silicon thin film layer 32Doping the thin film layer with phosphorus to obtain n-type FeSi2A film layer 4. Accordingly, FeSi connected to the p-type amorphous silicon thin film layer 72Doping boron in the thin film layer to obtain p-type FeSi2A film layer 6. With undoped FeSi2Thin film layer comparison, doped FeSi2The thin film layer can be better matched with the amorphous silicon thin film layer, so that the photon transmission efficiency is improved, and the light absorption utilization rate and the photoelectric conversion capacity of the cell are further improved.
It should be noted that the doping concentration will affect the open circuit voltage and short circuit current of the cell. Preferably, the n-type FeSi2The doping concentration of the thin film layer is 2 multiplied by 1018～3×1018cm-3. The p-type FeSi2The doping concentration of the thin film layer is 2 multiplied by 1017～3×1017cm-3. When the n-type FeSi is present2The doping concentration of the thin film layer is more than 3 multiplied by 1018cm-3The short circuit current of the battery is greatly reduced; when the n-type FeSi is present2The doping concentration of the thin film layer is less than 2 x 1018cm-3The open circuit voltage of the resulting battery is greatly reduced. The p-type FeSi2Doping concentration of thin film layer and n-type FeSi2The doping concentration of the thin film layer has similar change rules. Therefore, strict control of FeSi is required2Doping concentration of the thin film layer.
In step S3, the first intermediate obtained in step S2 is annealed, preferably at 500 to 800 ℃ for 30 to 90 seconds. More preferably, the annealing temperature is 600 ℃ and the annealing time is 60 s.
The annealing conditions were set to the obtained FeSi2The properties of the thin film layer have a significant impact. Specifically, first, the annealing temperature will affect the FeSi2FeSi in thin film layer2Phase type of crystal, alpha-FeSi with increasing annealing temperature2Increased phase content will result in beta-FeSi2The phase content is relatively reduced, so that FeSi is greatly reduced2Optical properties of the thin film layer. In addition, the annealing time will affect the FeSi obtained2Particle size and deposition effect, FeSi when the annealing time is > 90s2The particles are too large, and the silicon substrate is exposed, so that the deposition effect is poor. FeSi when the annealing time is less than 30s2alpha-FeSi in the thin film layer2Excessive-phase functional beta-FeSi2Too low a phase content results in the FeSi produced2The optical properties of the thin film layer are degraded.
In step S4, the p-type amorphous silicon thin film layer 7 and the n-type amorphous silicon thin film layer 3 are preferably prepared by glow discharge vapor deposition. Amorphous silicon has an order of magnitude greater light absorption coefficient near the peak of solar radiation than crystalline silicon. The forbidden band width is 1.7-1.8 eV, the mobility and minority carrier lifetime are far lower than those of crystalline silicon, and the open-circuit voltage of the cell can be effectively improved.
In step S5, the first transparent conductive layer 2 and the second transparent conductive layer 8 are one of a ZnO-based TCO film, a multi-element TCO film, and a high-mobility TCO film.
In the preparation process, the thickness of each thin film layer needs to be controlled, and the thickness of each thin film layer influences the photoelectric conversion efficiency of the cell. Preferably, the thickness of the monocrystalline silicon substrate layer 5 is 100-190 μm; the n-type FeSi2The thickness of the thin film layer 4 is 30-200 nm; the thickness of the n-type amorphous silicon thin film layer 3 is 5-20 nm; the p-type FeSi2The thickness of the thin film layer 6 is 30-200 nm; the thickness of the p-type amorphous silicon thin film layer 7 is 5-20 nm. Under the condition, the prepared solar cell has high light absorption efficiency.
Preferably, the monocrystalline silicon substrate layer 5 is a p-type monocrystalline silicon substrate or an n-type monocrystalline silicon substrate.
When the monocrystalline silicon substrate layer 5 is a p-type monocrystalline silicon substrate, preferably, the thickness of the p-type monocrystalline silicon substrate layer is 160-170 μm; the n-type FeSi2The thickness of the thin film layer 4 is 110-130 nm; the thickness of the n-type amorphous silicon thin film layer 3 is 10-20 nm; the p-type FeSi2The thickness of the thin film layer 6 is 80-100 nm; the thickness of the p-type amorphous silicon thin film layer 7 is 10-20 nm.
More preferably, the thickness of the p-type monocrystalline silicon substrate layer is 160 μm; the n-type FeSi2The thickness of the thin film layer 4 is 110 nm; the thickness of the n-type amorphous silicon thin film layer 3 is 15 nm; the p-type FeSi2The thickness of the thin film layer 6 is 90 nm; the thickness of the p-type amorphous silicon thin film layer 7 is 15 nm.
When the monocrystalline silicon substrate layer 5 is an n-type monocrystalline silicon substrate, preferably, the thickness of the n-type monocrystalline silicon substrate layer is 160-170 μm; the n-type FeSi2The thickness of the thin film layer 4 is 90-110 nm; the thickness of the n-type amorphous silicon thin film layer 3 is 5-15 nm; the p-type FeSi2The thickness of the thin film layer 6 is 90-110 nm; the thickness of the p-type amorphous silicon thin film layer 7 is 5-15 nm.
More preferably, the thickness of the n-type monocrystalline silicon substrate layer is 150 mu m; the n-type FeSi2The thickness of the thin film layer 4 is 100 nm; the thickness of the n-type amorphous silicon thin film layer 3 is 10 nm; the p-type FeSi2The thickness of the thin film layer 6 is 100 nm; the thickness of the p-type amorphous silicon thin film layer 7 is 10 nm.
The n-type amorphous silicon thin film layer 3 and the n-type FeSi layer2Thin film layer 4, monocrystalline silicon substrate layer 5, p-type FeSi2The thicknesses of the thin film layer 6 and the p-type amorphous silicon thin film layer 7 need to be comprehensively considered, and finally the optimal radiation absorption rate can be achieved. The thickness of the monocrystalline silicon substrate layer 5 influences the photovoltaic characteristics, and the thickness of the monocrystalline silicon substrate layer is thicker, so that photo-generated carriers disappear in the transportation process, cannot reach the upper surface and the lower surface of the cell, cannot be collected, and finally the photovoltaic characteristics are lost. The amorphous silicon thin film layer and FeSi2The thickness of the thin film layer will also affect the light absorption effect.
In addition, the n-type FeSi2The thin film layer 4 is the main light absorbing layer and is the main emission region, the thickness and doping of whichThe concentration has a significant effect on the cell performance. The internal quantum efficiency is closely related to the emitter thickness. When the n-type FeSi is present2Too thin a thickness of the thin film layer 4 may not sufficiently absorb photons in the long wavelength band, and photons greater than 1100nm are transparent to the crystalline silicon of the base region, so that photons greater than 1100nm are wasted. When the n-type FeSi is present2Too thick a thin film layer 4 will cause some of the photogenerated carriers to have been recombined before they have been collected, reducing the probability of collecting the photogenerated carriers. The n-type FeSi in the invention2When the thickness of the thin film layer 4 is not within the range of 30-200 nm, the light effect of absorbing incident light with the wavelength of about 1500nm cannot be achieved.
Correspondingly, the invention provides silicon-based FeSi prepared by the preparation method2Thin film quantum well solar cell, said FeSi2The thin film quantum well solar cell is provided with a front electrode layer 1, a first transparent conducting layer 2, an n-type amorphous silicon thin film layer 3 and an n-type FeSi layer from top to bottom in sequence2Thin film layer 4, monocrystalline silicon substrate layer 5, p-type FeSi2A thin film layer 6, a p-type amorphous silicon thin film layer 7, a second transparent conductive layer 8 and a back electrode layer 9. Wherein beta-FeSi2Is a direct band gap semiconductor material, has a forbidden band width of 0.87eV, and has the remarkable characteristic of large light absorption coefficient (larger than 105 cm)-1) The crystal silicon is about 100 times of the crystal silicon, most of sunlight can be absorbed only by a thin material, particularly, the absorption capacity to infrared light is strong, the response limit of the sunlight can be expanded to 1400nm, the utilization rate of solar spectrum can be obviously improved, the photoelectric theory conversion efficiency is high, the consumption of raw materials is obviously reduced, and the production cost is favorably reduced. In order to improve and expand the absorption limit of sunlight, the invention respectively arranges crystalline silicon/FeSi on the front surface and the back surface of the monocrystalline silicon substrate layer 52Amorphous silicon quantum well structure, compared with the structure that only the front side of the monocrystalline silicon substrate layer 5 or only the back side of the monocrystalline silicon substrate layer 5 is provided with crystalline silicon/FeSi2Amorphous silicon quantum well structure and silicon-based FeSi provided by the invention2The thin film quantum well solar cell can greatly expand the absorbable incident light wavelength and can achieve the absorption wavelength of about 1500nmAnd the incident light absorption utilization rate is obviously improved by emitting light, and the photoelectric conversion capability under weak light is improved.
The invention is further illustrated by the following specific examples:
example 1
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell comprises the following steps:
s1, cleaning and texturing the monocrystalline silicon substrate;
s2, preparing n-type FeSi on the front side of the monocrystalline silicon substrate2A thin film layer on the back of the single crystal silicon substrate to prepare p-type FeSi2Thin film layer to obtain FeSi with n-type2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A first intermediate of the thin film layer structure;
s3, annealing the first intermediate
S4, n-type FeSi in the first intermediate2Preparing an n-type amorphous silicon thin film layer 3 on the surface of the thin film layer, and preparing p-type FeSi of the first intermediate2Preparing a p-type amorphous silicon thin film layer on the back surface of the thin film layer to obtain the 3/n-type FeSi thin film layer with the n-type amorphous silicon2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A second intermediate of the thin film layer/p-type amorphous silicon thin film layer structure;
s5, preparing a first transparent conductive layer on the surface of the n-type amorphous silicon thin film layer 3 of the second intermediate, and preparing a second transparent conductive layer on the surface of the p-type amorphous silicon thin film layer of the second intermediate;
and then preparing a front electrode layer on the surface of the first transparent conducting layer, and preparing a back electrode layer on the surface of the second transparent conducting layer to obtain a finished product.
In step S2, the FeSi is prepared by plasma sputtering2A thin film layer;
wherein the n-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is 1: 3: 7;
the p-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is 1: 4: 5.
the background vacuum pressure of the plasma sputtering system is 8 x 10 before the preparation of the plasma sputtering-6mbar。
In the plasma sputtering preparation process, the reaction pressure of the plasma sputtering system is 5 x 10-3mbar; the flow rate of Ar gas is 200 sccm; the plasma generation power is 1500 w; the sputtering power is 300 w; the target application voltage is 200 v; the substrate heating temperature was 200 ℃.
In step S3, the annealing temperature is 600 ℃, and the annealing time is 60S.
Prepared silicon-based FeSi2In a thin-film quantum-well solar cell,
the thickness of the p-type monocrystalline silicon substrate layer is 160 mu m;
the n-type FeSi2The thickness of the thin film layer is 120 nm;
the thickness of the n-type amorphous silicon thin film layer is 15 nm;
the p-type FeSi2The thickness of the thin film layer is 90 nm;
the thickness of the p-type amorphous silicon thin film layer is 15 nm.
The n-type FeSi2The doping concentration of the thin film layer is 2 multiplied by 1018cm-3. The p-type FeSi2The doping concentration of the thin film layer is 2 multiplied by 1017cm-3。
Example 2
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell comprises the following steps:
s1, cleaning and texturing the monocrystalline silicon substrate;
s2, preparing n-type FeSi on the front side of the monocrystalline silicon substrate2A thin film layer on the back of the single crystal silicon substrate to prepare p-type FeSi2Thin film layer to obtain FeSi with n-type2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A first intermediate of the thin film layer structure;
s3, annealing the first intermediate
S4, n-type FeSi in the first intermediate2Preparing an n-type amorphous silicon thin film layer 3 on the surface of the thin film layer, and forming a p-type amorphous silicon thin film layer on the first intermediateForm FeSi2Preparing a p-type amorphous silicon thin film layer on the back surface of the thin film layer to obtain the 3/n-type FeSi thin film layer with the n-type amorphous silicon2Thin film layer/monocrystalline silicon substrate layer/p-type FeSi2A second intermediate of the thin film layer/p-type amorphous silicon thin film layer structure;
s5, preparing a first transparent conductive layer on the surface of the n-type amorphous silicon thin film layer 3 of the second intermediate, and preparing a second transparent conductive layer on the surface of the p-type amorphous silicon thin film layer of the second intermediate;
and then preparing a front electrode layer on the surface of the first transparent conducting layer, and preparing a back electrode layer on the surface of the second transparent conducting layer to obtain a finished product.
In step S2, the FeSi is prepared by plasma sputtering2A thin film layer;
wherein the n-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is 1: 2: 8;
the p-type FeSi2The film layer adopts Fe, Si and Ni combined target materials to provide raw materials, wherein Fe: si: the ratio of Ni is 1: 2: 6.
the background vacuum pressure of the plasma sputtering system is 8 x 10 before the preparation of the plasma sputtering-6mbar。
In the plasma sputtering preparation process, the reaction pressure of the plasma sputtering system is 5 x 10-3mbar; the flow rate of Ar gas is 200 sccm; the plasma generation power is 1500 w; the sputtering power is 300 w; the target application voltage is 200 v; the substrate heating temperature was 200 ℃.
In step S3, the annealing temperature is 600 ℃, and the annealing time is 60S.
Prepared silicon-based FeSi2In a thin-film quantum-well solar cell,
the thickness of the p-type monocrystalline silicon substrate layer is 150 micrometers;
the n-type FeSi2The thickness of the thin film layer is 100 nm;
the thickness of the n-type amorphous silicon thin film layer is 10 nm;
the p-type FeSi2The thickness of the thin film layer is 100 nm;
the thickness of the p-type amorphous silicon thin film layer is 10 nm.
The n-type FeSi2The doping concentration of the thin film layer is 3 multiplied by 1018cm-3. The p-type FeSi2The doping concentration of the thin film layer is 3 multiplied by 1017cm-3。
Example 3
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell is different from the embodiment 1 in the annealing process, wherein the annealing process comprises the following steps: the annealing temperature is 600 ℃, and the annealing time is 120 s.
Example 4
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell is different from that of the embodiment 1 in that the annealing process comprises the following steps: the annealing temperature is 600 ℃, and the annealing time is 20 s.
Example 5
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell is different from that of the embodiment 1 in that the annealing process comprises the following steps: the annealing temperature is 900 ℃, and the annealing time is 60 s.
Example 6
Silicon-based FeSi2The preparation method of the thin film quantum well solar cell is different from that of the embodiment 1 in that the annealing process comprises the following steps: the annealing temperature is 400 ℃, and the annealing time is 60 s.
Comparative example 1
A method for manufacturing a solar cell, comprising:
s1, cleaning and texturing the monocrystalline silicon substrate;
s2, preparing an n-type amorphous silicon thin film layer on the front side of the monocrystalline silicon substrate, and preparing a p-type amorphous silicon thin film layer on the back side of the monocrystalline silicon substrate;
s3, preparing a first transparent conducting layer on the surface of the n-type amorphous silicon thin film layer, and preparing a second transparent conducting layer on the surface of the p-type amorphous silicon thin film layer;
and then preparing a front electrode layer on the surface of the first transparent conducting layer, and preparing a back electrode layer on the surface of the second transparent conducting layer to obtain a finished product.
The solar cells prepared in the examples 1-6 and the comparative example 1 are subjected to volt-ampere characteristic test, the light with the wavelength of 1300-1600 nm is adopted for the test, the test results are shown in the table 1, and the results show that the silicon-based FeSi provided by the invention2The thin film quantum well solar cell has high photoelectric conversion efficiency.
Table 1 voltammetric measurements of solar cells prepared in examples 1-7
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
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