CN106299131B - SPPs film heterojunction and the solar cell of perovskite lamination and preparation method thereof - Google Patents

SPPs film heterojunction and the solar cell of perovskite lamination and preparation method thereof Download PDF

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CN106299131B
CN106299131B CN201610841268.7A CN201610841268A CN106299131B CN 106299131 B CN106299131 B CN 106299131B CN 201610841268 A CN201610841268 A CN 201610841268A CN 106299131 B CN106299131 B CN 106299131B
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spps
perovskite
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CN106299131A (en
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史林兴
周朕
黄增光
丁瑞强
孙庆强
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Huaihai Institute of Techology
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Abstract

The present invention discloses a kind of SPPs film heterojunction and solar cell of perovskite lamination and preparation method thereof, and the construction of the solar cell is from bottom to up are as follows: aluminium electrode；SPPs thin-film heterojunction solar cell；ITO articulamentum；Triangular grating perovskite battery；Metal grid lines electrode, the preparation method of the solar cell include the following steps: step 1: preparation SPPs thin film heteroj junction battery；Step 2: ITO articulamentum is prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system；Step 3: preparing triangular grating perovskite battery；Step 4: metal grid lines electrode is prepared using silk screen print method.Solar cell prepared by the present invention, short wavelength's sunlight is absorbed first with perovskite top battery, recycles film heterojunction bottom battery to absorb long wavelength's sunlight, constitutes reasonable stacked thin film batteries structure, the spectral absorption range for effectively having widened hull cell, improves photoelectric conversion efficiency.

Description

SPPs film heterojunction and the solar cell of perovskite lamination and preparation method thereof
Technical field
The invention belongs to novel laminated technical field of solar cells, are related to a kind of based on SPPs film heterojunction and perovskite Stacked solar cell, cascade solar cell combined and preparation method thereof.
Background technique
In finished product silica-based solar cell cost share, silicon materials account for nearly 40%, and the thickness of thin film solar cell Less than 1 μm, the 1/100 of insufficient crystal-silicon solar cell thickness, this is greatly lowered manufacturing cost.However, thickness reduces Reduce the efficiency of thin film solar cell simultaneously.The structure of " electricity is thin " " light is thick " may be implemented by light regime design, in turn Improve cell photoelectric transfer efficiency.
It is the most effectual way for improving cell photoelectric transfer efficiency using light trapping structure in all light regimes design.It receives The development of rice photonic material and nanometer manufacturing technology brings enormous motivation to the new sunken light mode of research, brilliant based on photon Surface plasma excimer (the Surface plasmon of the micro-nano structures such as body, diffraction grating and metal Nano structure Polaritons, SPPs) thin film solar cell also comes into being.
Optical absorption can only be improved in certain specific wave bands using the light regime design of light trapping structure, meanwhile, use list The theoretical efficiency of one light-sensitive material battery is determined that there are certain theoretical limits by the band gap width of this kind of material.However, utilizing The light-sensitive material of different band gap widths constitutes more knot laminated cells from top to down according to the size of band gap width to improve the sun The photoelectric conversion efficiency of battery is widely used.
Utilize CH3NH3PbI3Perovskite is that the efficiency of solar cell of light-sensitive material has reached 20% or more, in the battery table Face also can be further improved its transfer efficiency using nanostructure modification, however, since its band gap is 1.55eV, spectral absorption model It encloses and is confined between 300-800nm, spectrum in the near infrared region is not fully utilized.Crystal silicon band gap is 1.12eV, Its spectral absorption range preferably matches between 300-1100nm with perovskite band-gap energy, however, in the light of 800-1100nm Absorption is weaker in spectral limit, and light should can be effectively improved in the absorption of the wave band by being imitated using SPPs guided wave.Therefore, will have The perovskite battery of triangular grating structure prepares laminated cell in conjunction with SPPs thin film heteroj junction battery, can significantly improve thin The photoelectric conversion efficiency of film battery.
Summary of the invention
The object of the present invention is to provide a kind of based on triangular grating perovskite battery and SPPs thin film heteroj junction battery Laminated film solar battery technology and preparation method thereof widens spectral absorption range to the maximum extent, improves the laminate film sun The photoelectric conversion efficiency of battery, it is proposed that following technical solution:
A kind of solar cell of SPPs film heterojunction and perovskite lamination, the solar cell is from top to bottom successively are as follows: Aluminium electrode；SPPs thin-film heterojunction solar cell；ITO articulamentum；Triangular grating perovskite battery；Metal grid lines electrode.
Further improvement of these options, the SPPs thin-film heterojunction solar cell, from bottom to top successively are as follows: triangle Shape silver nanoparticle grating, conformal Si3N4Separation layer, conformal N+Type amorphous silicon layer, conformal intrinsic amorphous silicon layer, n type single crystal silicon layer, sheet Levy amorphous silicon layer and P+Type amorphous silicon layer.
Further improvement of these options, the triangular grating perovskite battery, from bottom to top successively are as follows: ZnO electricity Sub- transport layer, the CH with triangular grating structure3NH3PbI3Calcium titanium ore bed, conformal structure Spiro-OMeTAD hole transport Layer, conformal structure MoO3Interface-modifying layer, conformal structure ito transparent electrode.
A kind of preparation method of the solar cell of SPPs film heterojunction and perovskite lamination described in above scheme, it is described The preparation step of solar cell is as follows:
Step 1: preparation SPPs thin film heteroj junction battery:
A: preparing vee gutter using ultra-short pulse laser micro Process method in the front of commercially available ultra thin single crystalline silicon wafer, using flying Second laser micro-machining system carries out cable architecture processing to vee gutter；Existed using radio frequency plasma enhancing chemical vapour deposition technique H2Diluted SiH4One layer of intrinsic amorphous silicon layer is deposited in gas；Then in B2H6、H2And SiH4One layer of weight is deposited in mixed gas Adulterate P+Type amorphous silicon layer；
B: preparing vee gutter using ultra-short pulse laser micro Process method at the back side of monocrystalline silicon piece, micro- using femtosecond laser System of processing carries out cable architecture processing to vee gutter；Enhance one layer of chemical vapor deposition altogether using radio frequency plasma Shape intrinsic amorphous silicon layer；Then in PH3And H2Diluted SiH4One layer of conformal N of heavy doping is deposited in mixed gas+Type amorphous silicon Layer；
C: in conformal N+Type amorphous silicon layer surface is total using the enhancing chemical vapour deposition technique preparation of above-mentioned radio frequency plasma Shape Si3N4Separation layer；In conformal Si3N4Triangular Silver nanometer grating is prepared using silk screen print method on separation layer；Finally, using Silk screen print method prepares aluminium electrode in SPPs film heterojunction cell backside；
Step 2: ITO articulamentum is prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system；
Step 3: preparing triangular grating perovskite battery, magnetron sputtering is used on the ITO articulamentum of step (2) preparation Method prepares conformal ZnO electron transfer layer；CH is prepared on the ZnO electron transfer layer using two step infusion methods3NH3PbI3Calcium titanium Ore bed；Conformal structure Spiro-OMeTAD hole transmission layer is prepared on the calcium titanium ore bed using spin-coating method；Using thermal evaporation Method prepares conformal structure MoO on the hole transport layer3Interface-modifying layer；Finally, being prepared using magnetron sputtering coating system Conformal structure ito transparent electrode；
Step 4: metal grid lines electrode is prepared using silk screen print method.
Further improvement of these options, in the A of step (1), using femtosecond laser parallel micromachining system to triangle When slot carries out cable architecture processing, femtosecond laser energy 0.1-0.2mW, platform movement speed is 0.01-0.05mm/s, obtained The period of vee gutter is 220-280nm, base diameter 220-280nm, is highly 500-1000nm；The intrinsic amorphous of preparation Silicon layer with a thickness of 2-8nm；The P of preparation+Type amorphous silicon layer with a thickness of 5-15nm, doping concentration is 1 × 1018-1×1020cm-3。
Further improvement of these options, in the B of step (1), using femtosecond laser parallel micromachining system to triangle When slot carries out cable architecture processing, femtosecond laser energy 0.1-0.2mW, platform movement speed is 0.01-0.03mm/s, preparation The period of vee gutter is 600-900nm, bottom width 600-900nm, depth 150-250nm；It is obtained conformal intrinsic Amorphous silicon layer with a thickness of 2-8nm；Conformal N obtained+Type amorphous silicon layer with a thickness of 5-15nm, doping concentration is 1 × 1018-1 ×1020cm-3。
Further improvement of these options, in the C of step (1), conformal Si obtained3N4Separation layer with a thickness of 5- 20nm；Triangular Silver nanometer grating obtained, period 600-900nm, bottom width 600-900nm are highly 150- 250nm；Aluminium electrode obtained with a thickness of 100-150nm.
Further improvement of these options, in step (2), ITO articulamentum obtained with a thickness of 15-25nm.
Further improvement of these options prepares CH in step (3)3NH3PbI3The two step infusion method of method of calcium titanium ore bed Specifically: the spin coating PbI in glove box2Layer, the sample after spin coating is immersed in the aqueous isopropanol (MAI) of methylpyridinium iodide ammonium Sample is rinsed (MAI solution concentration: 40mg/mL) with isopropanol solvent after immersion by 3~5min, then will prepare Sample places 70~90 DEG C of 10~15min of drying on hot plate, then adjusts the temperature to 150 DEG C, continue drying 15~ 20min。
Further improvement of these options, in step (3), conformal ZnO electron transfer layer obtained with a thickness of 30- 60nm；CH obtained3NH3PbI3Calcium titanium ore bed with a thickness of 500-1200nm；The hole conformal structure Spiro-OMeTAD obtained Transport layer with a thickness of 150-200nm；Conformal structure MoO obtained3Interface-modifying layer with a thickness of 10-15nm；It is obtained total Shape structure I TO transparent electrode with a thickness of 80-120nm；In step (4), metal grid lines electrode obtained with a thickness of 150- 200nm。
It is obtained by the present invention the utility model has the advantages that
(1) the perovskite top battery of triangular grating structure proposed by the present invention can fully absorb 300-800nm spectrum Incident sunlight in range improves the photoelectric conversion efficiency of conventional perovskite battery.
(2) SPPs film heterojunction battery structure proposed by the present invention can use the raising of surface plasma bulk effect Light absorption in 800-1100nm spectral region improves the photoelectric conversion efficiency of bottom battery while reducing silicon materials usage amount.
(3) proposed by the present invention to be based on SPPs thin film heteroj junction battery and perovskite battery stack solar cell, first with Perovskite top battery absorbs short wavelength's sunlight, and film heterojunction bottom battery is recycled to absorb long wavelength's sunlight, and it is reasonable to constitute Stacked thin film batteries structure, effectively widened the spectral absorption range of hull cell, improved photoelectric conversion efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell of the present invention.
Fig. 2 is the preparation flow figure of the solar cell of SPPs film heterojunction of the present invention and perovskite lamination.
Fig. 3 is that the absorption spectrum of the solar cell of the present invention based on SPPs film heterojunction and perovskite lamination shows It is intended to.
Appended drawing reference: aluminium electrode -1；Triangular Silver nanometer grating -2；Conformal Si3N4Separation layer -3；Conformal N+Type amorphous silicon Layer -4；Conformal intrinsic amorphous silicon layer -5, n type single crystal silicon layer -6, intrinsic amorphous silicon layer -7；P+Type amorphous silicon layer -8；ITO connection Layer -9；ZnO electron transfer layer -10；CH3NH3PbI3Calcium titanium ore bed -11；Conformal structure Spiro-OMeTAD hole transmission layer -12； Conformal structure MoO3Interface-modifying layer -13；Conformal structure ito transparent electrode -14；Metal grid lines electrode -15.
Specific embodiment
To be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, below with reference to Specific embodiment, the present invention is further explained.
Embodiment 1
In conjunction with attached structural schematic diagram shown in FIG. 1, the present embodiment provides a kind of SPPs film heterojunction and perovskite laminations Solar cell, the solar cell is from top to bottom successively are as follows: aluminium electrode 1；SPPs thin-film heterojunction solar cell；ITO connection Layer 9；Triangular grating perovskite battery；Metal grid lines electrode 15.Wherein the SPPs thin-film heterojunction solar cell from lower and On successively are as follows: Triangular Silver nanometer grating 2, conformal Si3N4Separation layer 3, conformal N+Type amorphous silicon layer 4, conformal intrinsic amorphous silicon layer 5, n type single crystal silicon layer 6, intrinsic amorphous silicon layer 7 and P+Type amorphous silicon layer 8.The triangular grating perovskite battery is from bottom to top Successively are as follows: ZnO electron transfer layer 10, the CH with triangular grating structure3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro- OMeTAD hole transmission layer 12, conformal structure MoO3Interface-modifying layer 13, conformal structure ito transparent electrode 14.
In conjunction with attached flow chart shown in Fig. 2, the present embodiment also provides a kind of SPPs film heterojunction and perovskite lamination The preparation method of solar cell, preparation step are as follows:
Step 1: preparation SPPs thin film heteroj junction battery is sequentially prepared conformal in commercially available 6 front of N-type ultra thin single crystalline silicon wafer Levy amorphous silicon layer 7 and P+Type amorphous silicon layer 8 overleaf prepares triangle cutting, is sequentially prepared conformal intrinsic amorphous silicon layer 5 and N+ Then type amorphous silicon layer 4 prepares conformal Si3N4Separation layer 3 prepares silver-colored grating 2 in vee gutter, finally prepares aluminium electrode 1；
A: above-mentioned commercially available ultra thin single crystalline silicon wafer 6 with a thickness of 5um, the front of monocrystalline silicon piece 6 is micro- using ultra-short pulse laser Processing method prepares vee gutter, carries out cable architecture processing, femtosecond laser energy to vee gutter using femtosecond laser parallel micromachining system Amount is 0.1mW, and platform movement speed is 0.01mm/s, and the period that vee gutter is prepared is 220nm, and base diameter is 220nm is highly 500nm；Using radio frequency plasma enhancing chemical vapour deposition technique in H2Diluted SiH4One layer of sheet of middle deposition Amorphous silicon layer 7 is levied, with a thickness of 2nm；Then in B2H6、H2And SiH4One layer of heavy doping P is deposited in mixed gas+Type amorphous silicon layer 8, With a thickness of 5nm, doping concentration is 1 × 1018cm-3；
B: vee gutter is prepared using ultra-short pulse laser micro Process method at the back side of monocrystalline silicon piece 6, utilizes femtosecond laser Micro-machining system carries out cable architecture processing, femtosecond laser energy 0.1mW to vee gutter, and platform movement speed is 0.01mm/ S, the period that vee gutter is prepared is 600nm, bottom width 600nm, depth 150nm；Using radio frequency plasma Enhance one layer of chemical vapor deposition conformal intrinsic amorphous silicon layer 5, with a thickness of 2nm；Then in PH3And H2Diluted SiH4 One layer of conformal N of heavy doping is deposited in mixed gas+Type amorphous silicon layer 4, with a thickness of 5nm, doping concentration is 1 × 1018cm-3。
C: in conformal N+4 surface of type amorphous silicon layer is prepared conformal using radio frequency plasma enhancing chemical vapor deposition Si3N4Separation layer 3, with a thickness of 5nm；Triangular Silver nanometer grating 2 is prepared using silk screen print method, period 600nm, bottom is wide Degree is 600nm, is highly 150nm；Finally, aluminium electrode 1 is prepared in SPPs film heterojunction cell backside using silk screen print method, With a thickness of 100nm；
Step 2: ITO articulamentum, thickness are prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system For 15nm；
Step 3: preparing triangular grating perovskite battery, conformal ZnO electronics is sequentially prepared on ITO articulamentum 9 and is passed Defeated layer 10, CH3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro-OMeTAD hole transmission layer 12, MoO3Interface-modifying layer 13, Ito transparent electrode 14；
Conformal ZnO electron transfer layer 10 is prepared using magnetron sputtering method first on above-mentioned ITO articulamentum 9, with a thickness of 30nm；CH is prepared on ZnO electron transfer layer 10 using two step infusion methods3NH3PbI3Calcium titanium ore bed 11, the calcium titanium ore bed Two step infusion method of preparation method specifically: the spin coating PbI in glove box2Layer, is immersed in methylpyridinium iodide ammonium for the sample after spin coating Aqueous isopropanol (MAI) in 3min, sample is rinsed (MAI solution concentration: 40mg/ with isopropanol solvent after immersion ML), the sample prepared is then placed into 70 DEG C of drying 10min on hot plate, then adjusts the temperature to 150 DEG C, continues to dry Dry 15min, calcium titanium ore bed obtained with a thickness of 500nm；Conformal structure is prepared on calcium titanium ore bed 11 using spin-coating method Spiro-OMeTAD hole transmission layer 12, with a thickness of 150nm；Conformal structure is prepared on hole transmission layer 12 using thermal evaporation MoO3Interface-modifying layer 13, with a thickness of 10nm；Finally, preparing conformal structure ito transparent electrode using magnetron sputtering coating system 14, with a thickness of 80nm；
Step 4: metal grid lines electrode 15 being prepared using silk screen print method, with a thickness of 150nm.
Embodiment 2
In conjunction with attached structural schematic diagram shown in FIG. 1, the present embodiment provides a kind of SPPs film heterojunction and perovskite laminations Solar cell, the solar cell is from top to bottom successively are as follows: aluminium electrode 1；SPPs thin-film heterojunction solar cell；ITO connection Layer 9；Triangular grating perovskite battery；Metal grid lines electrode 15.Wherein the SPPs thin-film heterojunction solar cell from lower and On successively are as follows: Triangular Silver nanometer grating 2, conformal Si3N4Separation layer 3, conformal N+Type amorphous silicon layer 4, conformal intrinsic amorphous silicon layer 5, n type single crystal silicon layer 6, intrinsic amorphous silicon layer 7 and P+Type amorphous silicon layer 8.The triangular grating perovskite battery is from bottom to top Successively are as follows: ZnO electron transfer layer 10, the CH with triangular grating structure3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro- OMeTAD hole transmission layer 12, conformal structure MoO3Interface-modifying layer 13, conformal structure ito transparent electrode 14.
In conjunction with attached flow chart shown in Fig. 2, the present embodiment also provides a kind of SPPs film heterojunction and perovskite lamination The preparation method of solar cell, preparation step are as follows:
Step 1: preparation SPPs thin film heteroj junction battery is sequentially prepared conformal in commercially available 6 front of N-type ultra thin single crystalline silicon wafer Levy amorphous silicon layer 7 and P+Type amorphous silicon layer 8 overleaf prepares triangle cutting, is sequentially prepared conformal intrinsic amorphous silicon layer 5 and N+ Then type amorphous silicon layer 4 prepares conformal Si3N4Separation layer 3 prepares silver-colored grating 2 in vee gutter, finally prepares aluminium electrode 1；
A: above-mentioned commercially available ultra thin single crystalline silicon wafer 6 with a thickness of 8um, the front of monocrystalline silicon piece 6 is micro- using ultra-short pulse laser Processing method prepares vee gutter, carries out cable architecture processing, femtosecond laser energy to vee gutter using femtosecond laser parallel micromachining system Amount is 0.15mW, and platform movement speed is 0.03mm/s, and the period that vee gutter is prepared is 250nm, and base diameter is 250nm is highly 750nm；Using radio frequency plasma enhancing chemical vapour deposition technique in H2Diluted SiH4One layer of sheet of middle deposition Amorphous silicon layer 7 is levied, with a thickness of 5nm；Then in B2H6、H2And SiH4One layer of heavy doping P is deposited in mixed gas+Type amorphous silicon layer 8, With a thickness of 10nm, doping concentration is 1 × 1019cm-3；
B: vee gutter is prepared using ultra-short pulse laser micro Process method at the back side of monocrystalline silicon piece 6, utilizes femtosecond laser Micro-machining system process to vee gutter cable architecture, femtosecond laser energy 0.15mW, and platform movement speed is 0.02mm/ S, the period that vee gutter is prepared is 750nm, bottom width 750nm, depth 200nm；Using radio frequency plasma Enhance one layer of chemical vapor deposition conformal intrinsic amorphous silicon layer 5, with a thickness of 5nm；Then in PH3And H2Diluted SiH4 One layer of conformal N of heavy doping is deposited in mixed gas+Type amorphous silicon layer 4, with a thickness of 10nm, doping concentration is 1 × 1019cm-3。
C: in conformal N+4 surface of type amorphous silicon layer is prepared conformal using radio frequency plasma enhancing chemical vapor deposition Si3N4Separation layer 3, with a thickness of 15nm；Triangular Silver nanometer grating 2 is prepared using silk screen print method, period 750nm, bottom is wide Degree is 750nm, is highly 200nm；Finally, aluminium electrode 1 is prepared in SPPs film heterojunction cell backside using silk screen print method, With a thickness of 125nm；
Step 2: ITO articulamentum, thickness are prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system For 20nm；
Step 3: preparing triangular grating perovskite battery, and conformal ZnO electronics is sequentially prepared on ITO articulamentum 9 and is passed Defeated layer 10, CH3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro-OMeTAD hole transmission layer 12, MoO3Interface-modifying layer 13, Ito transparent electrode 14；
Conformal ZnO electron transfer layer 10 is prepared using magnetron sputtering method first on above-mentioned ITO articulamentum 9, with a thickness of 45nm；CH is prepared on ZnO electron transfer layer 10 using two step infusion methods3NH3PbI3Calcium titanium ore bed 11, the calcium titanium ore bed Two step infusion method of preparation method specifically: the spin coating PbI in glove box2Layer, is immersed in methylpyridinium iodide ammonium for the sample after spin coating Aqueous isopropanol (MAI) in 4min, sample is rinsed (MAI solution concentration: 40mg/ with isopropanol solvent after immersion ML), the sample prepared is then placed into 80 DEG C of drying 12min on hot plate, then adjusts the temperature to 150 DEG C, continues to dry Dry 18min, calcium titanium ore bed obtained with a thickness of 900nm；Conformal structure is prepared on calcium titanium ore bed 11 using spin-coating method Spiro-OMeTAD hole transmission layer 12, with a thickness of 175nm；Conformal structure is prepared on hole transmission layer 12 using thermal evaporation MoO3Interface-modifying layer 13, with a thickness of 12nm；Finally, preparing conformal structure ito transparent electrode using magnetron sputtering coating system 14, with a thickness of 100nm；
Step 4: metal grid lines electrode 15 being prepared using silk screen print method, with a thickness of 175nm.
Embodiment 3
In conjunction with attached structural schematic diagram shown in FIG. 1, the present embodiment provides a kind of SPPs film heterojunction and perovskite laminations Solar cell, the solar cell is from top to bottom successively are as follows: aluminium electrode 1；SPPs thin-film heterojunction solar cell；ITO connection Layer 9；Triangular grating perovskite battery；Metal grid lines electrode 15.Wherein the SPPs thin-film heterojunction solar cell from lower and On successively are as follows: Triangular Silver nanometer grating 2, conformal Si3N4Separation layer 3, conformal N+Type amorphous silicon layer 4, conformal intrinsic amorphous silicon layer 5, n type single crystal silicon layer 6, intrinsic amorphous silicon layer 7 and P+ type amorphous silicon layer 8.The triangular grating perovskite battery is from bottom to top Successively are as follows: ZnO electron transfer layer 10, the CH with triangular grating structure3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro- OMeTAD hole transmission layer 12, conformal structure MoO3Interface-modifying layer 13, conformal structure ito transparent electrode 14.
In conjunction with attached flow chart shown in Fig. 2, the present embodiment also provides a kind of SPPs film heterojunction and perovskite lamination The preparation method of solar cell, preparation step are as follows:
Step 1: preparation SPPs thin film heteroj junction battery is sequentially prepared conformal in commercially available 6 front of N-type ultra thin single crystalline silicon wafer Levy amorphous silicon layer 7 and P+Type amorphous silicon layer 8 overleaf prepares triangle cutting, is sequentially prepared conformal intrinsic amorphous silicon layer 5 and N+ Then type amorphous silicon layer 4 prepares conformal Si3N4Separation layer 3 prepares silver-colored grating 2 in vee gutter, finally prepares aluminium electrode 1；
A: above-mentioned commercially available ultra thin single crystalline silicon wafer 6 with a thickness of 10um, the front of monocrystalline silicon piece 6 is micro- using ultra-short pulse laser Processing method prepares vee gutter, carries out cable architecture processing, femtosecond laser energy to vee gutter using femtosecond laser parallel micromachining system Amount is 0.2mW, and platform movement speed is 0.05mm/s, and the period that vee gutter is prepared is 280nm, and base diameter is 280nm is highly 1000nm；Using radio frequency plasma enhancing chemical vapour deposition technique in H2Diluted SiH4Middle one layer of deposition Intrinsic amorphous silicon layer 7, with a thickness of 8nm；Then in B2H6、H2And SiH4One layer of heavy doping P is deposited in mixed gas+Type amorphous silicon layer 8, with a thickness of 15nm, doping concentration is 1 × 1020cm-3；
B: vee gutter is prepared using ultra-short pulse laser micro Process method at the back side of monocrystalline silicon piece 6, utilizes femtosecond laser Micro-machining system carries out cable architecture processing, femtosecond laser energy 0.2mW to vee gutter, and platform movement speed is 0.03mm/ S, the period that vee gutter is prepared is 900nm, bottom width 900nm, depth 250nm；Using radio frequency plasma Enhance one layer of chemical vapor deposition conformal intrinsic amorphous silicon layer 5, with a thickness of 8nm；Then in PH3And H2Diluted SiH4 One layer of conformal N of heavy doping is deposited in mixed gas+Type amorphous silicon layer 4, with a thickness of 15nm, doping concentration is 1 × 1020cm-3。
C: in conformal N+4 surface of type amorphous silicon layer is prepared conformal using radio frequency plasma enhancing chemical vapor deposition Si3N4Separation layer 3, with a thickness of 20nm；Triangular Silver nanometer grating 2 is prepared using silk screen print method, period 900nm, bottom is wide Degree is 900nm, is highly 250nm；Finally, aluminium electrode 1 is prepared in SPPs film heterojunction cell backside using silk screen print method, With a thickness of 150nm；
Step 2: ITO articulamentum, thickness are prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system For 25nm；
Step 3: preparing triangular grating perovskite battery, and conformal ZnO electronics is sequentially prepared on ITO articulamentum 9 and is passed Defeated layer 10, CH3NH3PbI3Calcium titanium ore bed 11, conformal structure Spiro-OMeTAD hole transmission layer 12, MoO3Interface-modifying layer 13, Ito transparent electrode 14；
Conformal ZnO electron transfer layer 10 is prepared using magnetron sputtering method first on above-mentioned ITO articulamentum 9, with a thickness of 30- 60nm；CH is prepared on ZnO electron transfer layer 10 using two step infusion methods3NH3PbI3Calcium titanium ore bed 11, the calcium titanium ore bed Two step infusion method of preparation method specifically: the spin coating PbI in glove box2Layer, is immersed in methylpyridinium iodide ammonium for the sample after spin coating Aqueous isopropanol (MAI) in 5min, sample is rinsed (MAI solution concentration: 40mg/ with isopropanol solvent after immersion ML), the sample prepared is then placed into 90 DEG C of drying 15min on hot plate, then adjusts the temperature to 150 DEG C, continues to dry Dry 20min, calcium titanium ore bed obtained with a thickness of 1200nm；Conformal structure is prepared on calcium titanium ore bed 11 using spin-coating method Spiro-OMeTAD hole transmission layer 12, with a thickness of 200nm；Conformal structure is prepared on hole transmission layer 12 using thermal evaporation MoO3Interface-modifying layer 13, with a thickness of 15nm；Finally, preparing conformal structure ito transparent electrode using magnetron sputtering coating system 14, with a thickness of 120nm；
Step 4: metal grid lines electrode 15 being prepared using silk screen print method, with a thickness of 200nm.
SPPs film heterojunction described in embodiment 1-3 and triangular grating perovskite stacked solar cell, cascade solar cell are effectively widened The spectral absorption range of hull cell carries out sunykatuib analysis to the battery using Finite-Difference Time-Domain Method, obtains such as 3 institute of attached drawing Show that absorption spectrum distribution map, perovskite top battery fully absorb short wavelength's sunlight, film heterojunction bottom battery effectively absorbs length Wavelength sunlight constitutes reasonable stacked thin film batteries structure, improves photoelectric conversion efficiency.
Those of ordinary skill in the art it should be appreciated that more than embodiment be intended merely to illustrate the present invention, And be not used as limitation of the invention, as long as the change in spirit of the invention, to embodiment described above Change, modification will all be fallen in scope of the presently claimed invention.

Claims (10)

1. the preparation method of a kind of SPPs film heterojunction and triangular grating perovskite stacked solar cell, cascade solar cell, it is characterised in that: The preparation step of the solar cell is as follows:
Step 1: preparation SPPs thin film heteroj junction battery:
A: preparing vee gutter using ultra-short pulse laser micro Process method in the front of ultra thin single crystalline silicon wafer, micro- using femtosecond laser System of processing carries out cable architecture processing to vee gutter；Using radio frequency plasma enhancing chemical vapour deposition technique in H2It is diluted SiH4One layer of intrinsic amorphous silicon layer is deposited in gas；Then in B2H6、H2And SiH4One layer of heavy doping P is deposited in mixed gas+Type Amorphous silicon layer；
B: vee gutter is prepared using ultra-short pulse laser micro Process method at the back side of monocrystalline silicon piece, utilizes femtosecond laser parallel micromachining System carries out cable architecture processing to vee gutter；Enhance chemical vapor deposition one layer conformal using radio frequency plasma Levy amorphous silicon layer；Then in PH3And H2Diluted SiH4One layer of conformal N of heavy doping is deposited in mixed gas+Type amorphous silicon layer；
C: in conformal N+Type amorphous silicon layer surface is prepared conformal using above-mentioned radio frequency plasma enhancing chemical vapour deposition technique Si3N4Separation layer；In conformal Si3N4Triangular Silver nanometer grating is prepared using silk screen print method on separation layer；Finally, using silk Net print process prepares aluminium electrode in SPPs film heterojunction cell backside；
Step 2: ITO articulamentum is prepared in SPPs film heterojunction battery front side using magnetron sputtering coating system；
Step 3: preparing triangular grating perovskite battery, magnetron sputtering legal system is used on the ITO articulamentum of step (2) preparation Standby conformal ZnO electron transfer layer；CH is prepared on the ZnO electron transfer layer using two step infusion methods3NH3PbI3Calcium titanium ore bed； Using spin-coating method in the CH3NH3PbI3Conformal structure Spiro-OMeTAD hole transmission layer is prepared on calcium titanium ore bed；Using heat Evaporation prepares conformal structure MoO on the hole transport layer3Interface-modifying layer；Finally, using magnetron sputtering coating system Prepare conformal structure ito transparent electrode；
Step 4: metal grid lines electrode is prepared using silk screen print method.
2. the preparation method of a kind of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell according to claim 1, It is characterized in that: in the A of step (1), when carrying out cable architecture processing to vee gutter using femtosecond laser parallel micromachining system, femtosecond Laser energy is 0.1-0.2mW, and platform movement speed is 0.01-0.05mm/s, and the period of vee gutter obtained is 220- 280nm, base diameter 220-280nm are highly 500-1000nm；The intrinsic amorphous silicon layer of preparation with a thickness of 2-8nm；System Standby P+Type amorphous silicon layer with a thickness of 5-15nm, doping concentration is 1 × 1018-1×1020cm-3。
3. the preparation method of a kind of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell according to claim 1, It is characterized in that: in the B of step (1), when carrying out cable architecture processing to vee gutter using femtosecond laser parallel micromachining system, femtosecond Laser energy is 0.1-0.2mW, and platform movement speed is 0.01-0.03mm/s, and the period of the vee gutter of preparation is 600- 900nm, bottom width 600-900nm, depth 150-250nm；Conformal intrinsic amorphous silicon layer obtained with a thickness of 2- 8nm；Conformal N obtained+Type amorphous silicon layer with a thickness of 5-15nm, doping concentration is 1 × 1018-1×1020cm-3。
4. the preparation method of a kind of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell according to claim 1, It is characterized in that: in the C of step (1), conformal Si obtained3N4Separation layer with a thickness of 5-20nm；Triangular Silver nanometer obtained Grating, period 600-900nm, bottom width 600-900nm are highly 150-250nm；Aluminium electrode obtained with a thickness of 100-150nm。
5. the preparation method of a kind of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell according to claim 1, Be characterized in that: in step (2), ITO articulamentum obtained with a thickness of 15-25nm.
6. the preparation method of a kind of SPPs thin film heteroj and perovskite stacked solar cell, cascade solar cell according to claim 1, special Sign is: preparing CH in step (3)3NH3PbI3The two step infusion method of method of calcium titanium ore bed specifically: the spin coating in glove box PbI2Layer, is immersed in 3~5min in the aqueous isopropanol of methylpyridinium iodide ammonium for the sample after spin coating, is with concentration after immersion Sample is rinsed by the isopropanol solvent of 40mg/mL, and the sample prepared is then placed 70~90 DEG C of bakings on hot plate Dry 10~15min, then adjusts the temperature to 150 DEG C, continues 15~20min of drying.
7. the preparation method of a kind of SPPs film heterojunction and perovskite stacked solar cell, cascade solar cell according to claim 1, Be characterized in that: in step (3), conformal ZnO electron transfer layer obtained with a thickness of 30-60nm；CH obtained3NH3PbI3Calcium Titanium ore layer with a thickness of 500-1200nm；Conformal structure Spiro-OMeTAD hole transmission layer obtained with a thickness of 150- 200nm；Conformal structure MoO obtained3Interface-modifying layer with a thickness of 10-15nm；Conformal structure ito transparent electrode obtained With a thickness of 80-120nm；In step (4), metal grid lines electrode obtained with a thickness of 150-200nm.
8. the SPPs film heterojunction as prepared by claim 1-7 described in any item preparation methods and perovskite lamination are too Positive electricity pond, it is characterised in that: the solar cell is from top to bottom successively are as follows: aluminium electrode；SPPs thin-film heterojunction solar cell； ITO articulamentum；Triangular grating perovskite battery and metal grid lines electrode.
9. the solar cell of a kind of SPPs film heterojunction and perovskite lamination according to claim 8, it is characterised in that: The SPPs thin-film heterojunction solar cell, from bottom to top successively are as follows: Triangular Silver nanometer grating, conformal Si3N4Separation layer is total to Shape N+Type amorphous silicon layer, conformal intrinsic amorphous silicon layer, n type single crystal silicon layer, intrinsic amorphous silicon layer and P+Type amorphous silicon layer.
10. the solar cell of a kind of SPPs film heterojunction and perovskite lamination according to claim 8, feature exist In the triangular grating perovskite battery, from bottom to top successively are as follows: ZnO electron transfer layer, with triangular grating structure CH3NH3PbI3Calcium titanium ore bed, conformal structure Spiro-OMeTAD hole transmission layer, conformal structure MoO3It is interface-modifying layer, conformal Structure I TO transparent electrode.
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