CN102157614B - Method for improving performance of amorphous silicon/microcrystalline silicon tandem solar cell - Google Patents
Method for improving performance of amorphous silicon/microcrystalline silicon tandem solar cell Download PDFInfo
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- CN102157614B CN102157614B CN2011100282377A CN201110028237A CN102157614B CN 102157614 B CN102157614 B CN 102157614B CN 2011100282377 A CN2011100282377 A CN 2011100282377A CN 201110028237 A CN201110028237 A CN 201110028237A CN 102157614 B CN102157614 B CN 102157614B
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Abstract
The invention discloses a method for improving the performance of an amorphous silicon/microcrystalline silicon tandem solar cell. The method is characterized in that the method is realized by inserting a p-type amorphous silicon composite layer on the n/p interface between a top cell and a bottom cell of the amorphous silicon/microcrystalline silicon tandem solar cell, that is, the p-type amorphous silicon composite layer is inserted on the n/p interface of the tandem cell, wherein the n layer of the top cell of the tandem cell is an amorphous silicon layer and the p layer of the bottom cell of the tandem cell is a nano-silicon layer. The method has the following beneficial effects: the loss at the tunnelling composite junction of the tandem cell can be reduced; experimental results show that the threshold voltage of the tandem cell is equal to the sum of the threshold voltage of the sub-cells, indicating that photo-induced carriers do not accumulate at the tunnelling composite junction; and meanwhile, the method for adjusting the borane gas doping ratio and growth time of the p-type amorphous silicon composite layer has the advantages of simpleness and practicability and is easy to apply in the industrialized process.
Description
Technical field
The present invention relates to the silicon-based film solar cells technical field, relate in particular to a kind of method of improving amorphous silicon/microcrystalline silicon tandem solar cell performance, the method realizes by improving tunnelling composite junction interface.
Background technology
The silicon-base thin-film battery materials are economized, energy consumption is low, can prepare in glass, stainless steel and plastic, and can realize large tracts of land production.After becoming silicon-base thin-film battery, these characteristics further reduce the hope of solar cell cost.But amorphous silicon intrinsic layer can only the sunlight of absorbing wavelength below 750nm, and because the light-induced degradation effect, the stabilization efficiency of the amorphous silicon unijunction solar cell of now industrialization is still very low.The transformation efficiency that how to improve silicon-base thin-film battery becomes the key whether this battery can develop later on a large scale.
In the situation that the light-induced degradation problem of amorphous silicon material itself can not be resolved for the moment, the light abstraction width that the amorphous silicon/microcrystalline silicon tandem solar cell can be by the expansion battery and the thickness of attenuate amorphous silicon intrinsic layer improve transformation efficiency and the stability of silicon-base thin-film battery.In the amorphous silicon/microcrystalline silicon tandem battery, the junction of battery can form a reverse p/n knot at the bottom of amorphous silicon top battery and the microcrystal silicon, and this ties so-called tunnelling composite junction.When laminated cell was in running order, the light induced electron in the intrinsic layer and photohole can be respectively to n layer and the migrations of p layer under the effect of built.The light induced electron of tunnelling composite junction place top battery and the photohole of end battery must be compound fast at the interface at the tunnelling composite junction, in order to avoid form charge accumulated, weaken built, reduce the collection of photo-generated carrier.Increase tunnelling composite junction at the interface effective ways of recombination probability is exactly at the composite bed of a floor height defect state of growing at the interface.
The method of improving at present the tunnelling composite junction mainly contains following two aspects: the oxide (NbO that 1, inserts at the interface high defective at the tunnelling composite junction
x, TiO
xOr SiO
x), but NbO
x, TiO
xCan not prepare with PECVD; SiO
xGenerally pass through CO
2Plasma treatment or break vacuum expose atmosphere and obtain, and thickness is not easy control, and may infringement be arranged to battery at the bottom of the microcrystal silicon.When 2, leading lower carbon dope amorphous silicon material for the p layer of tunnelling composite junction for electricity, insert the higher amorphous silicon p layer of one deck conductance ratio p-type carbon dope amorphous silicon layer and improve the hole at the interface transmission.Electricity was led higher p-type nanometer silicon layer and was applied in the silicon thin-film battery in recent years.
The present invention also adopts electricity to lead higher p-type nanometer silicon layer as the p layer of tunnelling composite junction, be under the condition of nano-silicon at the p layer, the present invention adopts the p-type amorphous silicon as insert layer, reaches the compound at the interface purpose of control by doping ratio and the thickness that changes the p-type amorphous silicon composite.
Summary of the invention
The technical problem that (one) will solve
Main purpose of the present invention is to provide a kind of method of improving amorphous silicon/microcrystalline silicon tandem solar cell performance, to improve the performance of amorphous silicon/microcrystalline silicon tandem solar cell
(2) technical scheme
For achieving the above object, the technical solution used in the present invention is that n/p inserts at the interface the p-type amorphous silicon composite and realizes between amorphous silicon/microcrystalline silicon tandem solar cell top battery and end battery, namely the n of top battery layer be amorphous silicon, end battery p layer be nano-silicon laminated cell insert at the interface the p-type amorphous silicon composite at n/p.
In the such scheme, the method for described improvement amorphous silicon/microcrystalline silicon tandem solar cell performance comprises the steps:
Step 1: clean at the bottom of the stainless steel lining, put into the PECVD system and toast, and base vacuum is taken out by the PECVD system;
Step 2: successively n layer, microcrystal silicon i layer and the nano-silicon p layer of battery at the bottom of the deposition micro crystal silicon at the bottom of the described stainless steel lining;
Step 3: the nano-silicon p layer of battery deposition p-type amorphous silicon composite at the bottom of microcrystal silicon;
Step 4: after having deposited the p-type amorphous silicon composite, successively the n layer of deposition of amorphous silicon top battery, amorphous silicon i layer and nano-silicon p layer obtain the laminated cell structure again;
Step 5: behind this laminated cell structure cool to room temperature, this laminated cell structure is taken out from the PECVD system, with Grown by Magnetron Sputtering indium tin oxide top electrode.
In the such scheme, described in the step 1 base vacuum is taken out by the PECVD system, base vacuum is 10
-4Pa.
In the such scheme, the n layer of battery, microcrystal silicon i layer and nano-silicon p layer at the bottom of the deposition micro crystal silicon described in the step 2 are using plasma enhanced chemical vapor deposition technology at the bottom of the described stainless steel lining successively deposition growing n layer, microcrystal silicon i layer and p layer; Wherein n layer and p layer adopt radio frequency, and microcrystal silicon i layer adopts very high frequency(VHF), H
2/ SiH
4The hydrogen thinner ratio be 7～20, reaction pressure is 120Pa～150Pa, power density is 0.4W/cm
2～0.6W/cm
2, underlayer temperature is 180 ℃～250 ℃, reaction time 60min～100min, microcrystal silicon i layer thickness 1300nm～1700nm.
In the such scheme, the radio frequency that described n layer and p layer adopt is 13.56MHz, and the very high frequency(VHF) that microcrystal silicon i layer adopts is 60MHz.
In the such scheme, during the p-type amorphous silicon composite of deposition described in the step 3, the borane gases doping ratio of the nano-silicon p layer of battery is 0.67% at the bottom of the described microcrystal silicon, and thickness is 1 to 2nm.
In the such scheme, when depositing the amorphous silicon i layer of top battery in the step 4, the frequency of employing is radio frequency, and this rf frequency is 13.56MHz; H
2/ SiH
4The hydrogen thinner ratio be 4～10, reaction pressure is 120Pa～250Pa, power density is 0.03W/cm
2～0.06W/cm
2, underlayer temperature is 150 ℃～200 ℃, reaction time 45min～55min, i layer thickness 250nm～350nm.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, the present invention improves battery performance by the tunnelling composite junction interface of adopting the p-type amorphous silicon composite to improve the amorphous silicon/microcrystalline silicon tandem solar cell, be under the high electric admittance rice silicon strip spare at the p of tunnelling composite junction layer, insert at the interface the amorphous silicon composite of one deck p-type at the n/p of tunnelling composite junction, doping ratio and growth time by regulation and control p-type amorphous silicon composite can reach the purpose that improves and optimizates the tunnelling composite junction, be applied to the tunnelling composite junction after optimizing in the laminated cell after the opening to press and open the pressure sum no better than the sub-battery of amorphous silicon before the lamination and the sub-battery of microcrystal silicon of laminated cell.This tunnelling composite junction interface processing method is simple and easy to do, is convenient to promote the tunnelling composite junction that the doping ratio by regulating the p-type amorphous silicon composite and growth time just can obtain high-quality.
2, utilize the present invention, can reduce the loss at laminated cell tunnelling composite junction place, experimental result show opening of laminated cell press equal sub-battery open the pressure sum, the accumulation that tunnelling composite junction place does not produce photo-generated carrier is described.Regulate simultaneously the borane gases doping ratio of p-type amorphous silicon composite and the method for growth time and have simple advantage, be convenient to be applied in the commercial processes.
Description of drawings
Fig. 1 is the amorphous silicon/microcrystalline silicon tandem battery schematic diagram that adopts the p-type amorphous silicon composite;
Fig. 2 is that p-type amorphous silicon composite doping ratio is on the impact of tunnelling composite junction IV curve;
Fig. 3 is that p-type amorphous silicon composite sedimentation time is on the impact of tunnelling composite junction IV curve;
Fig. 4 adopts the light IV curve of the laminated cell that obtains after the p-type amorphous silicon composite of optimal conditions and the light IV curve comparison figure of the sub-battery before the lamination.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
The method of this improvement amorphous silicon/microcrystalline silicon tandem solar cell performance provided by the invention, insert at the interface the p-type amorphous silicon composite by n/p between amorphous silicon/microcrystalline silicon tandem solar cell top battery and end battery and realize, namely the n of top battery layer be amorphous silicon, end battery p layer be nano-silicon laminated cell insert at the interface the p-type amorphous silicon composite at n/p.
The method of this improvement amorphous silicon/microcrystalline silicon tandem solar cell performance provided by the invention specifically comprises the steps:
Step 1: clean at the bottom of the stainless steel lining, put into the PECVD system and toast, and base vacuum is taken out by the PECVD system;
Step 2: successively n layer, microcrystal silicon i layer and the nano-silicon p layer of battery at the bottom of the deposition micro crystal silicon at the bottom of the described stainless steel lining;
Step 3: the nano-silicon p layer of battery deposition p-type amorphous silicon composite at the bottom of microcrystal silicon;
Step 4: after having deposited the p-type amorphous silicon composite, successively the n layer of deposition of amorphous silicon top battery, amorphous silicon i layer and nano-silicon p layer obtain the laminated cell structure again;
Step 5: behind this laminated cell structure cool to room temperature, this laminated cell structure is taken out from the PECVD system, with Grown by Magnetron Sputtering indium tin oxide top electrode.
The used equipment of growing is plasma auxiliary chemical vapor deposition system (PECVD), the gas used of deposition battery be 99.99% high purity silane and high-purity hydrogen as reacting gas, be that the borine of 1% (using diluted in hydrogen) and 1% phosphine (using diluted in hydrogen) are as impurity gas with purity.The frequency of the radio-frequency power supply of the activated plasma of amorphous silicon intrinsic layer is 13.56MHz, and the frequency of the very high frequency(VHF) power supply of the activated plasma of microcrystalline silicon intrinsic layer is 60MHZ.
Be the amorphous silicon/microcrystalline silicon tandem battery structure figure of p-type amorphous silicon composite with reference to Fig. 1, the below introduces concrete growth technique of the present invention in detail:
Step 1: then flexible stainless steel substrate was boiled 5 minutes with deionized water with the liquid detergent scrub, use ultrasonic 5 minutes of supersonic cleaning machine; Use again deionized water rinsing; Boiled again 5 minutes, and used ultrasonic 5 minutes of supersonic cleaning machine; Flushing was boiled 5 minutes more again, used ultrasonic 5 minutes of supersonic cleaning machine.
Step 2: the substrate that cleans up is put into the PECVD system, and 300 ℃ of bakings are extracted into system background vacuum degree and are higher than 10
-4The Pa magnitude.
Step 3: the n layer of the sub-battery of deposition micro crystal silicon at first.Adopt radio frequency (13.56MHz), before the deposition, use first hydrogen plasma clean substrate surface 5 minutes; During deposition N layer, hydrogen thinner ratio (H
2/ SiH
4) be 30～50; Doping ratio (PH
3/ SiH
4) be 0.01-0.02; Reaction pressure is 250Pa～350Pa; Power density is 0.3W/cm
2～0.7W/cm
2Underlayer temperature is 230 ℃～280 ℃; Reaction time 3min～7min, the n layer thickness of growth is 20～25nm.
Step 4: the intrinsic layer of battery at the bottom of the deposition micro crystal silicon then, adopt very high frequency(VHF) (60MHz), hydrogen thinner ratio (H
2/ SiH
4) be 7～20, reaction pressure is 120Pa～150Pa, power density is 0.4W/cm
2～0.6W/cm
2, underlayer temperature is 180 ℃～250 ℃, reaction time 60min～100min, microcrystal silicon i layer thickness 1300nm～1700nm.
Step 5: the p layer that then deposits the tunnelling composite junction.Adopt radio frequency (13.56MHz), hydrogen thinner ratio (H
2/ SiH
4) be 80-100, reaction pressure is 550Pa～700Pa, power density is 0.8W/cm
2～1W/cm
2, underlayer temperature is 130 ℃～180 ℃, reaction time 3min～5min, and the p layer thickness of growth is 20-30nm.
Step 6: deposition p-type amorphous silicon composite.Adopt radio frequency (13.56MHz), hydrogen thinner ratio (H
2/ SiH
4) be 8-12, doping ratio (B
2H
6/ SiH
4) be 0.0007, reaction pressure is 120Pa～150Pa, power density is 0.1W/cm
2, underlayer temperature is 180 ℃～250 ℃, reaction time 10s.
Step 7: the n layer of deposition of amorphous silicon top battery, adopt radio frequency (13.56MHz), hydrogen thinner ratio (H
2/ SiH
4) be 4-12; Doping ratio (PH
3/ SiH
4) be 0.01-0.02; Reaction pressure is 150Pa～250Pa; Power density is 0.05W/cm
2～0.15W/cm
2Underlayer temperature is 180 ℃～220 ℃; Reaction time 3min～7min, the n layer thickness of growth is 20～25nm.
Step 8: the intrinsic layer of deposition of amorphous silicon top battery, adopt radio frequency (13.56MHz), hydrogen thinner ratio (H
2/ SiH
4) be 4-12, reaction pressure is 100Pa～250Pa, power density is 0.04W/cm
2～0.15W/cm
2, underlayer temperature is 150 ℃～200 ℃, reaction time 30min～60min, i layer thickness 250nm～400nm.
Step 9: the p layer of deposition of amorphous silicon top battery.Adopt radio frequency (13.56MHz), hydrogen thinner ratio (H
2/ SiH
4) be 80-100, reaction pressure is 550Pa～700Pa, power density is 0.8W/cm
2～1W/cm
2, underlayer temperature is 130 ℃～180 ℃, reaction time 3min～5min, and the p layer thickness of growth is 20-30nm.
Step 10: deposit completely, battery is taken out from the PECVD system, with Grown by Magnetron Sputtering indium tin oxide transparency electrode.
Can be used as two actual parameters of regulation and control tunnelling composite junction character for doping ratio that the p-type amorphous silicon composite is described and sedimentation time, on at the bottom of the stainless steel lining, prepared separately the tunnelling composite junction, change respectively doping ratio and the sedimentation time of p-type amorphous silicon composite, between the doping ratio (Fig. 2) of test p-type amorphous silicon composite and sedimentation time (Fig. 3) on the impact of tunnelling composite junction IV character.Doping ratio and the sedimentation time that can see the p-type amorphous silicon composite all have a significant impact the IV character of tunnelling composite junction.Can be seen that by Fig. 2 and Fig. 3 in the PECVD in this laboratory system, the optimum doping ratio of the p-type amorphous silicon composite of tunnelling composite junction and growth time are respectively 0.67% and 10s.
In order further to verify the result after above-mentioned best tunnelling composite junction is applied to laminated cell, the light IV of the sub-battery of the front amorphous silicon of lamination and the sub-battery of microcrystal silicon and the light IV of the laminated cell that adopts the tunnelling composite junction after optimizing have been carried out contrasting (Fig. 4).Can be seen that by Fig. 4 the pressure of seeing of laminated cell is 1.4V, the pressure of opening of non-matted crystal battery and the sub-battery of microcrystal silicon is respectively 0.89V and 0.52V before the lamination.Behind the lamination battery open press no better than the sub-battery of lamination the first two open the pressure sum, from opening the angle of pressure, tunnelling composite junction place does not almost produce the accumulation of photo-generated carrier, light induced electron and photohole have obtained compound fast and effectively.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. method of improving amorphous silicon/microcrystalline silicon tandem solar cell performance, it is characterized in that, the method is inserted at the interface the p-type amorphous silicon composite by n/p between amorphous silicon/microcrystalline silicon tandem solar cell top battery and end battery and is realized, be the n of top battery layer be amorphous silicon, end battery p layer be nano-silicon laminated cell insert at the interface the p-type amorphous silicon composite at n/p.
2. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 1 is characterized in that the method comprises the steps:
Step 1: clean at the bottom of the stainless steel lining, put into the PECVD system and toast, and base vacuum is taken out by the PECVD system;
Step 2: successively n layer, microcrystal silicon i layer and the nano-silicon p layer of battery at the bottom of the deposition micro crystal silicon at the bottom of the described stainless steel lining;
Step 3: the nano-silicon p layer of battery deposition p-type amorphous silicon composite at the bottom of microcrystal silicon;
Step 4: after having deposited the p-type amorphous silicon composite, successively the n layer of deposition of amorphous silicon top battery, amorphous silicon i layer and nano-silicon p layer obtain the laminated cell structure again;
Step 5: behind this laminated cell structure cool to room temperature, this laminated cell structure is taken out from the PECVD system, with Grown by Magnetron Sputtering indium tin oxide top electrode.
3. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 2 is characterized in that, described in the step 1 base vacuum is taken out by the PECVD system, and base vacuum is 10
-4Pa.
4. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 2, it is characterized in that, the n layer of battery, microcrystal silicon i layer and nano-silicon p layer at the bottom of the deposition micro crystal silicon described in the step 2 are using plasma enhanced chemical vapor deposition technology at the bottom of the described stainless steel lining successively deposition growing n layer, microcrystal silicon i layer and p layer; Wherein n layer and p layer adopt radio frequency, and microcrystal silicon i layer adopts very high frequency(VHF), H
2/ SiH
4The hydrogen thinner ratio be 7～20, reaction pressure is 120Pa～150Pa, power density is 0.4W/cm
2～0.6W/cm
2, underlayer temperature is 180 ℃～250 ℃, reaction time 60min～100min, microcrystal silicon i layer thickness 1300nm～1700nm.
5. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 4 is characterized in that, the radio frequency that described n layer and p layer adopt is 13.56MHz, and the very high frequency(VHF) that microcrystal silicon i layer adopts is 60MHz.
6. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 2, it is characterized in that, during the p-type amorphous silicon composite of deposition described in the step 3, the borane gases doping ratio of the nano-silicon p layer of battery is 0.67% at the bottom of the described microcrystal silicon, and thickness is 1 to 2nm.
7. the method for improvement amorphous silicon/microcrystalline silicon tandem solar cell performance according to claim 2 is characterized in that, when depositing the amorphous silicon i layer of top battery in the step 4, the frequency of employing is radio frequency, and this rf frequency is 13.56MHz; H
2/ SiH
4The hydrogen thinner ratio be 4～10, reaction pressure is 120Pa～250Pa, power density is 0.03W/cm
2～0.06W/cm
2, underlayer temperature is 150 ℃～200 ℃, reaction time 45min～55min, i layer thickness 250nm～350nm.
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| CN103022269A (en) * | 2011-09-22 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | P type amorphous semiconductor manufactured by utilizing boron doping to improve tunneling effect film |
| CN103022270A (en) * | 2011-09-26 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | Technology for manufactured SiOx film to improve tunneling effect of stacked solar film |
| CN103022271A (en) * | 2011-09-28 | 2013-04-03 | 吉富新能源科技(上海)有限公司 | NP interface for manufacturing P-type tunneling layer to improve double-layer stacked solar energy |
| CN103219429B (en) * | 2013-04-22 | 2016-06-01 | 浙江正泰太阳能科技有限公司 | Lamination solar cell and its preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166320A (en) * | 1998-03-19 | 2000-12-26 | Toyota Jidosha Kabushiki Kaisha | Tandem solar cell |
| CN101777593A (en) * | 2010-01-20 | 2010-07-14 | 景德镇陶瓷学院 | Non-crystalline/micro-crystalline silicon laminated solar battery with middle layer doping structure and manufacture method thereof |
| CN101807618A (en) * | 2010-04-03 | 2010-08-18 | 威海中玻光电有限公司 | Novel laminated film solar cell and manufacturing method thereof |
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2011
- 2011-01-26 CN CN2011100282377A patent/CN102157614B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166320A (en) * | 1998-03-19 | 2000-12-26 | Toyota Jidosha Kabushiki Kaisha | Tandem solar cell |
| CN101777593A (en) * | 2010-01-20 | 2010-07-14 | 景德镇陶瓷学院 | Non-crystalline/micro-crystalline silicon laminated solar battery with middle layer doping structure and manufacture method thereof |
| CN101807618A (en) * | 2010-04-03 | 2010-08-18 | 威海中玻光电有限公司 | Novel laminated film solar cell and manufacturing method thereof |
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