CN102361039B - Transparent conducting layer-based black silicon solar cell and preparation method thereof - Google Patents
Transparent conducting layer-based black silicon solar cell and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a transparent conducting layer-based black silicon solar cell. A structural layer of the black silicon solar cell comprises a silver anti-oxidation layer, an aluminum conducting layer, a P type silicon layer, a black silicon absorption layer and an indium tin oxide (ITO) transparent conducting layer, wherein the aluminum conducting layer is a positive electrode of the solar cell, and the ITO transparent conducting layer is a negative electrode of the solar cell. A preparation method for the transparent conducting layer-based black silicon solar cell comprises the following steps of: cleaning the P type silicon layer; preparing the aluminum conducting layer on one surface of the P type silicon layer by a direct-current sputtering method; preparing the silver anti-oxidation layer below the aluminum conducting layer by an ion beam sputtering method; putting a prepared sample into a sealing cavity, and machining the black silicon absorption layer on the surface, which is not subjected to film plating, of the P type silicon layer by using a femtosecond laser; putting the sample into a tubular atmosphere furnace, and annealing; and preparing the ITO transparent conducting layer above the black silicon absorption layer by the ion beam sputtering method. By the transparent conducting layer-based black silicon solar cell, the loss of energy transfer on the surface of the black silicon absorption layer can be reduced effectively, and the energy conversion efficiency of the black silicon solar cell can be improved substantially.
Description
Technical field
The present invention relates to a kind of preparation method of the black silicon solar cell based on transparency conducting layer.
Background technology
Solar energy is a kind of eco-friendly power source of green non-pollution, and its energy source is inexhaustible.As a kind of sustainable energy, solar energy will become the main force of following safe energy field.Therefore solar cell has good market prospects and using value as the main devices of luminous energy and electric energy conversion.
Black silicon solar cell is a kind of novel solar cell.Studies show that the intensive silicon post that its sensitive surface has one deck to form based on the micro-nano structure preparation, these silicon posts have extremely strong sunken luminous energy power, be that the sunlight of 200nm-2500nm surpasses and can be absorbed more than 90% for wave-length coverage, the strong absorbability of its wide spectrum has substantially exceeded general pyramid making herbs into wool face, therefore based on deceiving the solar cell of silicon as absorbed layer great development potentiality is arranged.
Though " black silicon " has the superabsorbent ability of wide spectral range, but the conversion efficiency of solar cell based on " black silicon " surface but is difficult to improve at present, high-conversion rate only is 16.8%, even does not reach the conversion efficiency that chemical method is made solar cell 24.7%.The reason that causes its low conversion efficiency mainly is to prepare the orderly arrangement that (mainly containing laser preparation method and electrochemical erosion method) destroyed the silicon face lattice in the process of deceiving silicon at present, causes " black silicon " surface electronic mobility low, and the energy transfer loss is big.The sensitive surface structure of present black silicon solar cell generally is at a certain distance, goes up directly deposition transverse metal grid line at " black silicon "; Then at black silicon face deposition of silica as passivation layer.Copy chemical photronic processing method that two drawbacks are arranged like this: the existence of (1) metal grid lines has covered certain black silicon absorbed layer area, causes reducing of effective light-receiving area.(2) black silicon face is damaged owing to lattice arrangement, the light induced electron that the low electron mobility that causes only makes the black silicon near the metal grid lines both sides produce can effectively be drawn, and the light induced electron that the black silicon of two grid line mid portions produces in migrating to the process of grid line with regard to approach exhaustion, cause the loss of energy.
Summary of the invention
The invention discloses a kind of preparation method of the black silicon solar cell based on transparency conducting layer, shortcomings such as its purpose is effectively to overcome the sensitive surface electron transfer proportion of goods damageds height that existing black silicon solar cell exists, and feasible " black silicon " conversion efficiency of solar cell is low.The present invention can not only effectively reduce black silicon absorbed layer surface energy transfer loss, promotes black silicon face electron mobility, and can significantly promote the energy conversion efficiency of black silion cell.
A kind of black silicon solar cell based on transparency conducting layer, be characterized in: structure sheaf is followed successively by from bottom to top: silver oxidation resistance layer, aluminium conductive layer, P type silicon layer, black silicon absorbed layer and ITO(indium tin oxide transparent conducting film) transparency conducting layer, wherein the aluminium conductive layer is the positive pole of solar cell, and the ITO transparency conducting layer is the negative pole of solar cell.
A kind of preparation method of the black silicon solar cell based on transparency conducting layer comprises the steps:
A) clean P type silicon layer: it is in the solution of 2:1 that P type silicon layer is placed acetone and absolute alcohol volume ratio, cleans 3min in supersonic wave cleaning machine; Again P type silicon layer being placed on concentration with deionized water rinsing is that 98% sulfuric acid, hydrogen peroxide, deionized water volume ratio are in the solution of 2:1:1, cleans 3min in supersonic wave cleaning machine; Use washed with de-ionized water after the taking-up again;
B) AM aluminum metallization conductive layer: will place in the vacuum chamber of the dc sputtering deposition machine that the aluminium target is housed through the P type silicon layer sample that cleans, vacuumize processing, be evacuated to vacuum degree and in vacuum chamber, feed argon gas less than after the 7*10E-4Pa, flow is opened dc sputtering power again between 10-100sccm, below P type silicon layer, power with 10 to 100w carries out plated film, the plated film time is 0.5 to 5 hour, forms metal electrode below the aluminium conductive layer, as the positive pole of black silicon solar cell;
C) evaporation silver oxidation resistance layer: will place through the sample of AM aluminum metallization conductive layer in the vacuum chamber of the ion beam sputtering deposition machine that silver-colored target is housed, and vacuumize processing, and be evacuated to vacuum degree less than 4*10E-3Pa; Feed argon gas afterwards in vacuum chamber, flow is opened the ion beam sputtering power supply again between 1-100sccm, and below the aluminium conductive layer, the line with 20 to 100ma carries out plated film, and the plated film time is 0.1 to 1 hour;
D) the black silicon absorbed layer of processing: will place in the annular seal space through the sample that evaporation silver oxidation resistance layer is handled, be evacuated to below the 4*10E-4Pa; In annular seal space, feed sulfur hexafluoride gas, make the annular seal space internal gas pressure between 2*10E4 to 8*10E4Pa; Place the P type silicon layer upper surface of sulfur hexafluoride gas with the irradiation of femto-second laser hot spot, make P type silicon layer upper surface be gone out to deceive the silicon pattern by laser ablation, sulfur hexafluoride gas decomposites sulphur simple substance under the irradiation of femtosecond laser, the silicon of part sulphur simple substance and black silicon face dissolves each other under the heat that high power laser light produces and forms the N-type layer, part sulphur simple substance is deposited on black silicon face, this part sulphur simple substance will be in next step short annealing further dissolves each other with the silicon of black silicon face, forms the N-type layer;
E) annealing: will place in the tubular type atmosphere furnace through the sample that the black silicon absorbed layer of processing is handled, in boiler tube, feed argon gas, flow is between 1 to 10000sccm, afterwards boiler tube is heated to 200 to 1500 degrees centigrade, time is between 10 minutes to 50 minutes, be deposited on the sulphur simple substance on black silicon absorbed layer surface and the silicon of black silicon face and dissolve each other, further form the N-type layer;
F) processing ITO transparency conducting layer: the sample of annealed processing is placed in the vacuum chamber of the ion beam sputtering deposition machine that the ITO target is housed, vacuumize processing, be evacuated to vacuum degree less than 4*10E-3Pa; In vacuum chamber, feed argon gas afterwards, flow is between 1-100sccm, aerating oxygen in the vacuum chamber afterwards, flow is between 1-100sccm, open the ion beam sputtering power supply afterwards, above black silicon absorbed layer, the line with 20 to 100ma carries out plated film, the plated film time is 2 to 4 hours, forms the ITO transparency conducting layer.
The present invention can not only effectively reduce black silicon absorbed layer surface energy transfer loss, promotes black silicon face electron mobility, and can significantly promote the energy conversion efficiency of black silicon solar cell.
Description of drawings
Fig. 1 is the black silicon solar cell structure schematic diagram that the present invention is based on transparency conducting layer.
1, ITO transparency conducting layer, 2, black silicon absorbed layer, 3, P type silicon layer, 4, the aluminium conductive layer, 5, the silver oxidation resistance layer.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in detail.
As shown in Figure 1: a kind of black silicon solar cell based on transparency conducting layer, structure sheaf is followed successively by from bottom to top: silver oxidation resistance layer 5, aluminium conductive layer 4, P type silicon layer 3, black silicon absorbed layer 2 and ITO transparency conducting layer 1, wherein the aluminium conductive layer is the positive pole of solar cell, and the ITO transparency conducting layer is the negative pole of solar cell.Concrete preparation method is as follows:
A) clean P type silicon layer: it is in the solution of 2:1 that P type silicon layer is placed acetone and absolute alcohol volume ratio, cleans 3min in supersonic wave cleaning machine, is used for removing P type silicon surface greasy dirt; With P type silicon layer deionized water rinsing, be used for removing acetone and alcohol residue again; Afterwards, it is that 98% sulfuric acid, hydrogen peroxide, deionized water volume ratio are the solution of 2:1:1 that P type silicon layer is placed concentration, cleans 3min in supersonic wave cleaning machine, is used for removing the oxide layer of P type silicon face; Afterwards, use washed with de-ionized water, it is residual be used for to remove sulfuric acid, hydrogen peroxide, acetone;
B) AM aluminum metallization conductive layer: will place in the vacuum chamber of the dc sputtering deposition machine that the aluminium target is housed through the silicon chip that cleans, vacuumize processing, be evacuated to vacuum degree less than 7*10E-4Pa; Feed argon gas afterwards in vacuum chamber, flow is used for gas as a setting between 10-100sccm; Open dc sputtering power afterwards, below P type silicon layer 3, the power with 10 to 100w carries out plated film, and the plated film time is 0.5 to 5 hour; Be used for below aluminium conductive layer 4, forming metal electrode, as the positive pole of black silicon solar cell;
C) evaporation silver oxidation resistance layer: will place through the sample of AM aluminum metallization conductive layer in the vacuum chamber of the ion beam sputtering deposition machine that silver-colored target is housed, and vacuumize processing, and be evacuated to vacuum degree less than 4*10E-3Pa; Feed argon gas afterwards in vacuum chamber, flow is used for gas as a setting between 1-100sccm; Open the ion beam sputtering power supply afterwards, below aluminium conductive layer 4, the line with 20 to 100ma carries out plated film, and the plated film time is 0.1 to 1 hour; Be used for isolated aluminium conductive layer and contact with air, the moisture in the external world, prevent the oxidation of aluminium conductive layer;
D) the black silicon absorbed layer of processing: will place in the annular seal space through the sample that evaporation silver oxidation resistance layer is handled, be evacuated to below the 4*10E-4Pa; In annular seal space, feed sulfur hexafluoride gas, make the annular seal space internal gas pressure between 2*10E4 to 8*10E4Pa; Shine P type silicon layer 3 upper surfaces that place sulfur hexafluoride gas with femto-second laser with certain spot size, make P type silicon layer 3 upper surfaces be gone out to deceive the silicon absorbed layer by laser ablation.Effect 1: the black silicon pattern of formation is used for absorbing wavelength at the light wave of 200nm-2500nm, has the absorbability that surpasses more than 90%, produces photo-generated carrier; Effect 2: sulfur hexafluoride gas decomposites sulphur simple substance under the irradiation of femtosecond laser, the silicon of part sulphur simple substance and black silicon face dissolves each other under the heat that high power laser light produces and forms the N-type layer, part sulphur simple substance is deposited on black silicon face, this part sulphur simple substance will be in next step short annealing further dissolves each other with the silicon of black silicon face, forms the N-type layer;
E) annealing: will place in the tubular type atmosphere furnace through the sample that the black silicon absorbed layer of processing is handled, in boiler tube, feed argon gas, flow is between 1 to 10000sccm, effect 1: be used for preventing silver oxidation resistance layer 5 high-temperature oxydation, effect 2: prevent from processing that the elemental sulfur on black silicon absorbed layer surface generates sulfur dioxide with oxygen reaction behind the black silicon absorbed layer, cause the sulphur loss; Afterwards boiler tube is heated to 200 to 1500 degrees centigrade, the time is between 10 minutes to 50 minutes.Effect 1: the sulphur simple substance that is deposited on black silicon absorbed layer 2 surfaces and the silicon of black silicon face are dissolved each other, further form the N-type layer; Effect 2: make between P type silicon layer 3 and the aluminium conductive layer 4 and form ohmic contact by annealing, the resistance between P type silicon layer 3 and the aluminium conductive layer 4 is reduced greatly, reduce the internal resistance of black silion cell; Effect 3: make to form the alloy-layer that dissolves each other between aluminium conductive layer 4 and the silver oxidation resistance layer 5, reduce charge carrier in the consumption that makes between aluminium conductive layer 4 and the silver oxidation resistance layer 5, further reduce the internal resistance of black silion cell; Effect 4: guaranteeing that the black constant prerequisite of the peculiar pattern of silicon absorbed layer is necessarily recovered the ruined silicon atom lattice arrangement in black silicon absorbed layer surface, effectively promotes black silicon face electron mobility;
F) processing ITO transparency conducting layer: the sample of annealed processing is placed in the vacuum chamber of the ion beam sputtering deposition machine that the ITO target is housed, vacuumize processing, be evacuated to vacuum degree less than 4*10E-3Pa; Feed argon gas afterwards in vacuum chamber, flow is used for gas as a setting between 1-100sccm; Aerating oxygen in the vacuum chamber afterwards, flow between 1-100sccm, be used for as with the reacting gas of ITO target; Open the ion beam sputtering power supply afterwards, above black silicon absorbed layer 2, the line with 20 to 100ma carries out plated film, and the plated film time is 2 to 4 hours, forms the ITO transparency conducting layer.Effect 1: utilize the good advantage of ITO material conductive characteristic, black silicon absorbed layer surface is directly contacted with the ITO film close, effectively reduce black silicon face energy transfer loss; Effect 2: utilize the hard and fine and close characteristics of ITO film, the micro-nano structure on the black silicon absorbed layer surface of protection is avoided outside destroy; Effect 3: utilize the high characteristics of ITO film light penetration, make light can see through ITO transparency conducting layer 1 and shine black silicon absorbed layer 2 surfaces, produce photo-generated carrier.
Claims (1)
1. the preparation method based on the black silicon solar cell of transparency conducting layer is characterized in that comprising the steps:
A) clean P type silicon layer: it is in the solution of 2:1 that P type silicon layer is placed acetone and absolute alcohol volume ratio, cleans 3min in supersonic wave cleaning machine; Again P type silicon layer being placed on concentration with deionized water rinsing is that 98% sulfuric acid, hydrogen peroxide, deionized water volume ratio are in the solution of 2:1:1, cleans 3min in supersonic wave cleaning machine; Use washed with de-ionized water after the taking-up again;
B) AM aluminum metallization conductive layer: will place in the vacuum chamber of the dc sputtering deposition machine that the aluminium target is housed through the P type silicon layer sample that cleans, vacuumize processing, be evacuated to vacuum degree and in vacuum chamber, feed argon gas less than after the 7*10E-4Pa, flow is opened dc sputtering power again between 10-100sccm, below P type silicon layer, power with 10 to 100w carries out plated film, the plated film time is 0.5 to 5 hour, forms metal electrode below the aluminium conductive layer, as the positive pole of black silicon solar cell;
C) evaporation silver oxidation resistance layer: will place through the sample of AM aluminum metallization conductive layer in the vacuum chamber of the ion beam sputtering deposition machine that silver-colored target is housed, and vacuumize processing, and be evacuated to vacuum degree less than 4*10E-3Pa; Feed argon gas afterwards in vacuum chamber, flow is opened the ion beam sputtering power supply again between 1-100sccm, and below the aluminium conductive layer, the line with 20 to 100ma carries out plated film, and the plated film time is 0.1 to 1 hour;
D) the black silicon absorbed layer of processing: will place in the annular seal space through the sample that evaporation silver oxidation resistance layer is handled, be evacuated to below the 4*10E-4Pa; In annular seal space, feed sulfur hexafluoride gas, make the annular seal space internal gas pressure between 2*10E4 to 8*10E4Pa; Place the P type silicon layer upper surface of sulfur hexafluoride gas with the irradiation of femto-second laser hot spot, make P type silicon layer upper surface be gone out to deceive the silicon pattern by laser ablation, sulfur hexafluoride gas decomposites sulphur simple substance under the irradiation of femtosecond laser, the silicon of part sulphur simple substance and black silicon face dissolves each other under the heat that high power laser light produces and forms the N-type layer, part sulphur simple substance is deposited on black silicon face, this part sulphur simple substance will be in next step short annealing further dissolves each other with the silicon of black silicon face, forms the N-type layer;
E) annealing: will place in the tubular type atmosphere furnace through the sample that the black silicon absorbed layer of processing is handled, in boiler tube, feed argon gas, flow is between 1 to 10000sccm, afterwards boiler tube is heated to 200 to 1500 degrees centigrade, time is between 10 minutes to 50 minutes, be deposited on the sulphur simple substance on black silicon absorbed layer surface and the silicon of black silicon face and dissolve each other, further form the N-type layer;
F) processing ITO transparency conducting layer: the sample of annealed processing is placed in the vacuum chamber of the ion beam sputtering deposition machine that the ITO target is housed, vacuumize processing, be evacuated to vacuum degree less than 4*10E-3Pa; In vacuum chamber, feed argon gas afterwards, flow is between 1-100sccm, aerating oxygen in the vacuum chamber afterwards, flow is between 1-100sccm, open the ion beam sputtering power supply afterwards, above black silicon absorbed layer, the line with 20 to 100ma carries out plated film, the plated film time is 2 to 4 hours, forms the ITO transparency conducting layer.
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| CN103367476B (en) * | 2012-03-27 | 2015-12-16 | 电子科技大学 | A kind of N +the black silicon new construction of/N-type and preparation technology |
| CN103681970A (en) * | 2013-12-18 | 2014-03-26 | 电子科技大学 | Method for manufacturing black silicon materials |
| CN104064502A (en) * | 2014-07-18 | 2014-09-24 | 余瑞琴 | Black silicon preparation technology combining ion beam surface activation sputtering and reactive-ion etching |
| CN105390909A (en) * | 2015-11-04 | 2016-03-09 | 上海无线电设备研究所 | Terahertz source based on intrinsic semiconductor layer with micro-nano structure and preparation method |
| CN105742407B (en) * | 2016-03-22 | 2017-08-11 | 电子科技大学 | A kind of method that black silicon is prepared in doping film layer |
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| CN101789466A (en) * | 2010-02-10 | 2010-07-28 | 上海理工大学 | Method for manufacturing solar battery |
| CN101789462A (en) * | 2010-02-24 | 2010-07-28 | 中国科学院半导体研究所 | Broad-spectrum absorption black silicon solar cell structure and preparation method thereof |
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