CN102637781A - Method for preparing amorphous silicon thin-film solar battery with nip structure - Google Patents
Method for preparing amorphous silicon thin-film solar battery with nip structure Download PDFInfo
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- CN102637781A CN102637781A CN2012101363978A CN201210136397A CN102637781A CN 102637781 A CN102637781 A CN 102637781A CN 2012101363978 A CN2012101363978 A CN 2012101363978A CN 201210136397 A CN201210136397 A CN 201210136397A CN 102637781 A CN102637781 A CN 102637781A
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Abstract
The invention discloses a method for preparing a silicon-based thin-film battery with a nip structure by using box type plasma enhanced chemical vapor deposition equipment, which relates to the field of vacuum coating methods and mainly solves the problem that an intrinsic i layer is influenced by residual phosphorus because doped phosphorus can not be thoroughly flushed in a technical method for preparing a battery with a nip structure. The method for preparing an amorphous silicon thin-film solar battery with a nip structure is characterized in that: three adjacent exciting electrodes are used as a group; the exciting electrode in the middle is used for preparing n, i and p layers in sequence, and after the n layer is prepared, the exciting electrode stops working; the two exciting electrodes adjacent to the exciting electrode in the middle turn on radio-frequency signals to generate a plasma filed to clean a plasma box; and after cleaning, the exciting electrode in the middle gets back to work to deposit the i and p layers in sequence. The method has simple steps and is low in implementation cost, and the pollution level of the intrinsic i layer is very low, so that the method can be widely used for preparing the battery with the nip structure.
Description
Technical field
The invention belongs to vacuum coating equipment and method field, be mainly concerned with the method that a kind of plasma enhanced chemical vapor deposition legal system is equipped with nip structure amorphous silicon thin-film solar cell.
Background technology
Bigger shortcoming of amorphous silicon membrane battery is exactly photo attenuation (a S-W effect).A method that suppresses photo attenuation is the thickness that reduces intrinsic layer, and this has drawn the notion of " many knots ", through several cell stack can be reduced the thickness of each sub-battery obsorbing layer together.If the absorbed layer to each sub-battery adopts the different materials that can be with, then solar spectrum can be absorbed more fully, thereby improves the efficient of entire cell.For the absorbed layer of narrow band gap, μ c-Si:H or a-SiGe:H are desirable material, all in the middle of practice, have received widely and having used.
Many knots photovoltaic device of popular based thin film silicon mainly is an a-Si:H/ μ c-Si:H binode battery in the industry, and it has an important disadvantages.Because nanocrystal silicon has indirect luminous energy band gap,, need a quite thick nanocrystal silicon intrinsic i layer in the binode, like 2000 nanometers in order to produce a large amount of photoelectric currents.But the nanocrystal silicon speed of growth that meets the device performance requirement is slow (like 9 nm/minute) very, and the large tracts of land deposition also needs very large complicated production equipment equably, and this equipment price is expensive, cause production cost to increase.Reduce the thickness of nanocrystal silicon i layer film or shorten its sedimentation time a-Si/nc-Si binode photovoltaic device to be compared with other designs do not have advantage.And for a-Si:H and a-SiGe:H battery, then not too high to the requirement of equipment, and a-Si:H/a-SiGe:H/ a-SiGe:H three junction batteries also are current international important development directions.Current, most effective genus a-Si:H/a-SiGe:H/a-SiGe:H three junction batteries in many knots of volume production silicon-base thin-film battery, the conversion efficiency after stable surpasses 13%.
The gas ions chemical vapor depsotition equipment abbreviates PECVD equipment as, and as depicted in figs. 1 and 2 is cheap box-type apparatus for plasma chemical vapor deposition sketch map in the middle of the silicon thin film industry in recent years.Its core is a packaged type plasma case, and it allows in the individual plasma reactor in the single vacuum chamber, all the non-doping on mass substrate in the electrooptical device of successive sedimentation simultaneously with the silicon thin film that mixes.As shown in Figure 1, plasma case 2 is made up of a plurality of exciting electrode 20A, 20B, 20C and a plurality of grounding electrode 21A, 21B, 21C, 21D, wherein the sidewall paneling of the grounding electrode 21A of both sides, 21D double as plasma case.All plate exciting electrodes and grounding electrode are assembled by parallel to each other and maintenance equidistantly.Exciting electrode and grounding electrode are alternately placed, and each all is clipped between the electrode of two opposite polarities, and spacing is 24mm.Place the substrate on the portion surface within it except that the sidewall grounding electrode, two flat surfaces of other all electrodes can be placed the substrate 8 that is used to plated film, normally glass substrate.In the coating process, produce glow discharge in the zone 7 between two adjacent electrodes, form plasma field.The quantity of the exciting electrode in the plasma case 2 can be any integer according to requirement of system design, normally 12 or 18, and three the enough explanation detailed processes of the present invention of here only drawing.The remainder insulated body polytetrafluoroethylene 6A of exciting electrode 20A, 20B, 20C and plasma case and 6B isolate.The cable 12 of conductively-closed is used to exciting electrode is connected on the radio-frequency power supply 13 of vacuum chamber 1 outside.The gas box at plasma case 2 tops (air distribution plate, shower nozzle) 3 is placed on all electrode tops, is that the aperture 5 of 1-2mm is evenly introduced the gas raw material dispersedly toward the zone between the adjacent electrode 7 through diameter.Door 15A and 15B be by the vertical two ends that are placed on electrode arrangement before and after two of plasma case, and be as shown in Figure 2, the flow direction of introducing gas in the gas ions zone is restricted to from top to bottom, and can not flow out the plasma case in the horizontal direction.The air inlet 4 on vacuum chamber 1 top is a metal hose, when air intake valve 30A opens opisthogenesis admixture of gas, for example silane (SiH
4), hydrogen (H
2) and germane (GeH
4) be introduced into the gas box 3 from the outside gas piping of vacuum chamber; From many holes 5 of gas box bottom, flow down then; Flow along interstitial area 7; Flow out to the space between plasma case 2 and vacuum chamber 1 inwall from the hollow space 10 of understructure 9, and under the state that the valve 30B that gives vent to anger opens, be discharged from vacuum chamber by gas outlet 14.Electric heater is attached on the wall of vacuum chamber 1, is used for improving or keeping the temperature of whole vacuum chamber 1 and plasma case 2.11 rollers for plasma case turnover vacuum chamber 1.
With the PECVD apparatus in comparison of other types, " box-type " PECVD equipment has cheaply, production capacity big and the gas effciency advantages of higher, and the amorphous silicon membrane battery cost performance of preparing is high.Yet, as the PECVD equipment of other single chambers,, can't prepare the amorphous silicon thin-film solar cell of the normal nip structure of performance though it can prepare the amorphous silicon thin-film solar cell of the pin structure of function admirable.Its reason is that the amorphous silicon intrinsic layer conduction type of growth in situ is weak n type; When the battery of preparation pin structure; Doped chemical boron major part in the p layer can be fallen with inert gas such as argon cleaning, and the part of remaining minute quantity can play suitable neutralization to intrinsic i layer, can improve the performance of battery; This has obtained confirmation in the amorphous silicon industry, even in intrinsic i layer, deliberately mixes boron element in the laboratory that has; And when the battery of preparation nip structure; Although the doped chemical phosphorus through cleaning in the n layer for a long time can be rinsed to a great extent; But the part that remains minute quantity still will produce significantly influence to intrinsic i layer, and directly has influence on the performance of battery.
Summary of the invention
For solving in the technical method that adopts single chamber PECVD equipment to prepare nip structure battery in the background technology owing to causing the residual phosphorus element that intrinsic i layer is produced significantly influence by cleaning down doped chemical phosphorus; And directly have influence on the problem of battery performance; The present invention aims to provide a kind of can reduce single cavity apparatus for plasma chemical vapor deposition and prepare nip structure battery the time, the battery preparation method that n layer doped chemical phosphorus pollutes intrinsic i layer.
For achieving the above object; The present invention adopts following technological means: a kind of method of the nip of preparation structure amorphous silicon thin-film solar cell; Its scheme is: adopt box-type PECVD equipment, in the preparation process, use the source mist that comprises silane, germane and hydrogen, the air pressure in the vacuum chamber maintains between 300mT-1000mT; Substrate is placed the surface of parallel plate electrode, and the temperature of substrate remains between 160-220 ℃.It is characterized in that: adopt the box-type apparatus for plasma chemical vapor deposition to prepare the amorphous silicon membrane battery of nip structure; Substrate can be a glass; Also can be that flexible substrate comprises at the bottom of the stainless steel lining or polymer substrate; During preparation nip structure battery; In the plasma case with three adjacent exciting electrodes as one group; That middle exciting electrode is used for preparing successively n, i, p layer, after the preparation of n layer finishes this exciting electrode quit work and with whole vacuum cavity in comprise that the reacting gas in the plasma case is replaced into the gas with etching function and makes vacuum cavity be in closed state, and two adjacent with it exciting electrodes are opened radiofrequency signals and are produced plasma fields and begin article on plasma body case and clean.Etching gas dynamic circulation under the closed state and P that absorption is gone up on each surface of plasma case and inside cavity etches away, and the n laminar surface is because Si-Si key bond energy is big combines closely, and the P under the Si-Si network is played a very good protection.Clean these two exciting electrodes that finish the next door, back and quit work, the gas that cleans usefulness is discharged cavity, feed reacting gas, and the exciting electrode of centre is resumed work, deposit i, p layer successively, preparation nip structure battery.For multijunction cell, after finishing, each n layer deposition all need repeat this cleaning.
Say that further the gas with etching function that is adopted is hydrogen.
Beneficial effect:
A, the method step that the present invention adopted are simple, utilize have cheap, production capacity is big and " box-type " PECVD equipment gas effciency advantages of higher prepares nip structure amorphous silicon thin-film solar cell, realizes that cost is low.
B, the prepared battery of the cleaning method that the present invention adopted and Ar carry out the prepared battery of normal developing and carry out quantum efficiency (QE) test comparison, and the contaminated degree of intrinsic i layer is very little.
C, the method that the present invention adopted are passed through after n layer deposition; Article on plasma body case carries out plasma clean before p, the i layer deposition; Eliminate the cross pollution of impurity element, and can not produce damage, prepare nip structure battery with normal performance to the n layer that has deposited to intrinsic i layer.
Description of drawings
Fig. 1 is a box-type PECVD equipment front view.
Fig. 2 is a box-type PECVD equipment side view.
Fig. 3 is with 15 minutes nip structure battery QE of Ar flushing test quantum efficiency curve diagram.
Fig. 4 is with 10 minutes nip structure battery QE of the inventive method flushing test quantum efficiency curve diagram.
Embodiment
As depicted in figs. 1 and 2, the present invention uses the box-type apparatus for plasma chemical vapor deposition to prepare the amorphous silicon membrane battery of nip structure.For the ease of describing, only provided here relate to one group of exciting electrode 20A of the present invention, 20B, 20C and with the corresponding grounding electrode 21A of exciting electrode, 21B, 21C, 21D.All substrates all adopt glass or flexible material; Wherein have only between two substrates, 20B and the 21C between 20B and the 21B two substrates totally four substrates be used for preparing battery; Back electrode Al that is coated with battery above and the ZnO:Al that plays sunken light action, and other substrate all adopts common inexpensive glass metal electrode board is played a protective role when the plasma clean.When preparation nip structure battery, exciting electrode 20B starts working, and on described four substrates, deposits n type amorphous silicon layer with general technology.After finishing, n layer deposition close exciting electrode 20B and with the gas H of the gas displacement in the vacuum cavity for Si and P are had the etching function
2, this gas is including, but not limited to H
2Valve-off 30A and 30B make vacuum cavity be in closed state fully when reaching certain air pressure such as 500mT in the vacuum chamber, and toward the radiofrequency signal of exciting electrode 20A with 20C feeding smaller power such as 50W.Produce a large amount of active group H in the plasma case 2 at this moment; Owing to exist certain temperature gradient thereby the gas under closed state meeting dynamic circulation in the vacuum cavity inevitably; This makes active group H wherein can plasma case and each surperficial P that goes up absorption of inside cavity be etched away; And the n laminar surface, plays a very good protection to the P under the Si-Si network in conjunction with closely because Si-Si key bond energy is big.Cleaned time enough as ten minutes after exciting electrode 20A and 20C quit work, it is clean with gaseous emission to open vacuum cavity valve 30B.Feed reacting gas then, exciting electrode 20B starts working, and deposits i layer and p layer successively by normal process conditions, prepares the electrode of nip structure.
Like Fig. 3 and shown in Figure 4, adopt the prepared battery of cleaning method of the present invention and carry out the prepared battery of normal developing with Ar and carry out quantum efficiency (QE) test, judge the effect of cleaning through the degrees of offset of relatively not having QE curve under reverse biased and the-2V reverse biased; Can see; If adopt Ar to carry out normal developing, the non-constant of cleaning performance then, battery need just can have preferably photo-generated carrier and collect under reverse biased; And if adopt cleaning method of the present invention; The degrees of offset of QE curve is very little under no reverse biased and the-2V reverse biased, shows that cleaning performance is very good, and the contaminated degree of intrinsic i layer is very little.
Claims (2)
1. method for preparing nip structure amorphous silicon thin-film solar cell; Its scheme is: adopt box-type PECVD equipment; In the preparation process, use the source mist that comprises silane, germane and hydrogen; Air pressure in the vacuum chamber maintains between 300mT-1000mT, substrate is placed the surface of parallel plate electrode, and the temperature of substrate remains between 160-220 ℃; It is characterized in that: on substrate, prepare non-crystal silicon solar cell; In the plasma case with three adjacent exciting electrodes as one group; That middle exciting electrode is used for preparing successively n, i, p layer, after the preparation of n layer finishes this exciting electrode quit work and with whole vacuum cavity in comprise that the reacting gas in the plasma case is replaced into the gas with etching function and makes vacuum cavity be in closed state, and two other exciting electrode is opened radiofrequency signal and is produced plasma field and begin article on plasma body case and clean; Cleaning these two exciting electrodes that finish the next door, back quits work; The gas that cleans usefulness is discharged cavity, feed reacting gas, and the exciting electrode of centre is resumed work; Deposit i, p layer successively, preparation nip structure battery; For multijunction cell, after finishing, each n layer deposition all need repeat this cleaning.
2. according to the said a kind of method for preparing nip structure amorphous silicon thin-film solar cell of claim 1, it is characterized in that: said gas with etching function is hydrogen.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104775106A (en) * | 2015-04-09 | 2015-07-15 | 山东禹城汉能薄膜太阳能有限公司 | Electrode plate of reaction box deposited with multiple PECVD (Plasma Enhanced Chemical Vapour Deposition) amorphous silicon membranes and amorphous silicon membrane deposition method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050205127A1 (en) * | 2004-01-09 | 2005-09-22 | Mitsubishi Heavy Industries Ltd. | Photovoltaic device |
| US20090255581A1 (en) * | 2008-04-10 | 2009-10-15 | Seung-Yeop Myong | Thin film silicon solar cell and manufacturing method thereof |
| CN101593792A (en) * | 2008-05-26 | 2009-12-02 | 福建钧石能源有限公司 | The manufacture method of thin-film solar cells |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050205127A1 (en) * | 2004-01-09 | 2005-09-22 | Mitsubishi Heavy Industries Ltd. | Photovoltaic device |
| US20090255581A1 (en) * | 2008-04-10 | 2009-10-15 | Seung-Yeop Myong | Thin film silicon solar cell and manufacturing method thereof |
| CN101593792A (en) * | 2008-05-26 | 2009-12-02 | 福建钧石能源有限公司 | The manufacture method of thin-film solar cells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104775106A (en) * | 2015-04-09 | 2015-07-15 | 山东禹城汉能薄膜太阳能有限公司 | Electrode plate of reaction box deposited with multiple PECVD (Plasma Enhanced Chemical Vapour Deposition) amorphous silicon membranes and amorphous silicon membrane deposition method |
| CN104775106B (en) * | 2015-04-09 | 2017-08-08 | 山东禹城汉能薄膜太阳能有限公司 | Multi-disc deposits the battery lead plate and amorphous silicon membrane deposition process of PECVD amorphous silicon membrane reaction boxes |
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Application publication date: 20120815 |