CN102956742A - Manufacturing method of solar cell - Google Patents
Manufacturing method of solar cell Download PDFInfo
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- CN102956742A CN102956742A CN2011102440604A CN201110244060A CN102956742A CN 102956742 A CN102956742 A CN 102956742A CN 2011102440604 A CN2011102440604 A CN 2011102440604A CN 201110244060 A CN201110244060 A CN 201110244060A CN 102956742 A CN102956742 A CN 102956742A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A manufacturing method of a solar cell includes: step A, etching a first conduction type substrate in a dry etching method, and allowing an incident face to be of a high-low fluctuation shape and provided with a plasma destruction layer; step B, oxidizing the plasma destruction layer to be converted into an oxide layer; step C, removing the oxide layer in a wet etching way; step D, performing thermal diffusion processing to form a second conduction type emitting layer. The plasma destruction layer is oxidized by the oxidation processing, so that before the thermal diffusion processing, a KOH (potassium hydroxide) etching step in a given method can be omitted, the oxide layer can be removed only by one-time wet etching, and accordingly processing time is greatly shortened, capacity is enhanced, and both feasibility of volume production and conversion efficiency of the solar cell can be taken into account.
Description
Technical field
The present invention relates to a kind of manufacture method of solar cell, particularly relate to a kind of manufacture method of carrying out the solar cell of the improved process for making behind the surface roughening with reactive ion etch (RIE) technology.
Background technology
The processing procedure of general silicon wafer solar cell is that silicon substrate with a p-type carries out thermal diffusion (thermal diffusion) and processes, and makes this substrate surface form the emitter layer of a N-shaped, and then forms the p-n junction.But when rough surface concavo-convex about the incidence surface of this battery is is found in research, can reduce light reflection, promote the ratio that light incides inside battery, and promote conversion efficiency.Therefore a kind of improvement processing procedure being arranged at present, is to utilize reactive ion etch (Reactive Ion Etching is called for short RIE) mode before diffusion process, etching substrate surface and form rough surface.
Consult Fig. 1, although the RIE processing procedure can etching substrates 11 and reach the demand of substrate 11 concave-convex surfaces, but therefore the charged particle in this processing procedure (plasma) also can react with substrate 11 materials, make substrate 11 surfaces form first-class ion damaged layer 12, the existence of these ion damaged layers 12 will increase charge carrier again in conjunction with rate (Recombination), thereby can reduce the photoelectric conversion efficiency of solar cell, so after the RIE processing procedure, must remove these ion damaged layers 12 by the Wet-type etching mode again, because the material of plasma breakable layer 12 is with silicon (Si), oxide (the SiO of silicon
X) be main, usually must carry out twice etching and just can remove, be respectively with hydrofluoric acid (HF) etching solution etching SiO
X, and with potassium hydroxide (KOH) etching solution etching Si.After these ion damaged layers 12 remove, carry out again heat diffusion treatment to form the p-n junction.
And the shortcoming of above-mentioned processing procedure is: when using KOH etching Si, because due to the characteristic of Si itself, the temperature when etching and KOH concentration all will precisely be controlled, and the Si of predetermined thickness could be removed, but about the control between the thickness of Si and etch temperature, the concentration, and be not easy to control.In addition, when carrying out Wet-type etching, to first substrate 11 be moved on to etching in the etching bath that is full of KOH solution, then again substrate 11 is moved on to the etching bath etching that another is full of HF solution, because substrate 11 is moved on to etching bath need to expend time in, above-mentioned processing procedure is to carry out Wet-type etching twice in two different etching baths still more, so the 11 spent times of moving substrate will increase to twice, therefore its processing procedure time is long, production efficiency is low, is unfavorable for industrial production.And above-mentioned for carrying out the etching of KOH and HF, need to adopt two etching machines just can carry out, so the cost of board equipment can significantly increase, and will cause the problem of cost control on the volume production, and two equipment also produce the problem that occupies more space on plant area's production line.
Summary of the invention
The object of the present invention is to provide a kind of shortening processing procedure time, and can take into account the manufacture method of the solar cell of battery conversion efficiency and volume production demand.Thereby the problem that can reduce the cost of equipment purchase and avoid occupying too much plant area production line space.
The manufacture method of solar cell of the present invention comprises:
Steps A: utilize dry-etching mode etching one first conductivity type substrate, make an incidence surface of this first conductivity type substrate become the shape that just rises and falls, and this incidence surface also forms a plasma breakable layer;
Step B: these ion damaged layers of oxidation make these ion damaged layers be transformed into an oxide layer;
Step C: utilize the Wet-type etching mode to remove this oxide layer;
Step D: this first conductivity type substrate is carried out heat diffusion treatment, make the incidence surface of this first conductivity type substrate form second a conductivity type emitter layer, to finish the semi-finished product of making this solar cell; And
Step e: the semi-finished product at this solar cell form electrode.
Method of the present invention, the oxidizing temperature of step B are 300 ℃～500 ℃.
Method of the present invention, the thickness of this oxide layer are 5 nanometers～10 nanometers.
Method of the present invention, the oxidization time of step B are 1 minute～25 minutes.
Method of the present invention, the dry-etching of steps A utilizes the reactive ion etch mode.
Method of the present invention, the material of this oxide layer comprises the oxide of silicon, and the etching solution of step C Wet-type etching is hydrofluoric acid solution.
Method of the present invention also comprises one and is positioned at step D step F afterwards, forms an anti-reflecting layer at this second conductivity type emitter layer, and step e forms described electrode on the surface of this anti-reflecting layer and the surface of this first conductivity type substrate.
Method of the present invention, the heat diffusion treatment of step D also can make a side of this first conductivity type substrate form a semiconductor layer, then recycle the Wet-type etching mode and remove this semiconductor layer.
Method of the present invention is hydrofluoric acid solution for the etching solution that removes this semiconductor layer.
The main charge carrier of described the first conductivity type substrate and this second conductivity type emitter layer must not limit, as long as can form the p-n junction, therefore when this first conductivity type substrate was the p-type semiconductor, this second conductivity type emitter layer was the N-shaped semiconductor; When this first conductivity type substrate was the N-shaped semiconductor, this second conductivity type emitter layer was the p-type semiconductor.
Described oxidizing temperature for these ion damaged layers of oxidation is 300 ℃～500 ℃, and oxidization time is 1～25 minute, and making formed oxidated layer thickness is 5 nanometers (nm)～10 nanometers.Wherein, the essential lower limit that limits of oxidizing temperature is because when temperature is too low, because temperature is not enough, can't make reactant gas molecules produce enough mobile kinetic energy, will cause this reacting gas fully to react and oxidation with these ion damaged layers; And oxidizing temperature just can reach abundant oxidation effectiveness in 500 ℃, does not need temperature to be raise again, and also just causes energy waste because improve temperature again.In addition, owing to this oxidation process is that the continue dry-etching of this steps A carries out, and two steps are to carry out in same vacuum cavity, and cavity temperature roughly all maintains 300 ℃～500 ℃, therefore oxidizing temperature must additionally not change again, and is quite convenient in the making.
The present invention is for the restriction of oxidization time, also be in order to make these ion damaged layers can fully react oxidation, need to prove, the oxidation rate of these ion damaged layers is along with the increase of oxidization time will be slack-off gradually, so can bring into play the highest oxidation efficiency in the oxidization time in the early stage, oxidization time does not need oversize.
Beneficial effect of the present invention is: by carry out oxidation process behind the RIE processing procedure, the plasma breakable layer is oxidized to oxide layer, make the present invention before heat diffusion treatment, can omit the KOH etching step, and only needing Wet-type etching once is removable this oxide layer, significantly reduce the processing procedure time, promote production capacity, can take into account the feasibility of volume production and the conversion efficiency of solar cell.
Description of drawings
Fig. 1 is a kind of schematic diagram of part-structure of known solar cells;
Fig. 2 is a schematic diagram, the solar cell that the preferred embodiment of the manufacture method of demonstration solar cell of the present invention manufactures;
Fig. 3 is the schematic diagram of each step of this preferred embodiment when carrying out;
Fig. 4 is the steps flow chart calcspar of this preferred embodiment.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
Consult Fig. 2, the preferred embodiment of manufacture method of the present invention, for the manufacture of a solar cell, described solar cell comprises that one first conductivity type substrate 2, one are positioned at the electrode 6 that the second conductivity type emitter layer 4 on the incidence surface 21 of this first conductivity type substrate 2, are positioned at the surface of anti-reflecting layer 5 on this second conductivity type emitter layer 4 and two lower surfaces that lay respectively at this first conductivity type substrate 2 and anti-reflecting layer 5, and the delivery of electrical energy that described electrode 6 is used for battery is produced is to outside.
Consult Fig. 3, Fig. 4, the manufacture method of solar cell of the present invention comprises:
(1) carry out step 71: prepare this first conductivity type substrate 2, present embodiment is p-type semiconductor silicon (Si) substrate.
(2) carry out step 72: the surface that utilizes this first conductivity type substrate 2 of dry-etching mode etching, present embodiment is to use reactive ion etch (Reactive Ion Etching, be called for short RIE) mode, its concrete grammar is in the vacuum cavity of a RIE equipment, cavity temperature is about 300 ℃～500 ℃, and passes into SF
6, Cl
2And O
2Mist makes the incidence surface 21 of the first conductivity type substrate 2 form the shape that just rises and falls as reacting gas, namely forms concavo-convex coarse micro-structural (Texturing).And because the surface of this first conductivity type substrate 2 can produce reaction with plasma, so also can form a plasma breakable layer 3 on this incidence surface 21, these ion damaged layer 3 materials are mainly the oxide (SiO of silicon (Si) and silicon
x).
(3) carry out step 73: with aforementioned SF
6And Cl
2Air flow source close, in vacuum cavity, only pass into O
2Gas, O
2Being provoked in cavity is that oxygen plasma also continues and these ion damaged layers 3 reactions, and then these ion damaged layer 3 oxidations are transformed into an oxide layer 3 ', and its material is mainly SiO
xIn this oxidizing process, this cavity temperature namely oxidizing temperature is about 300 ℃～500 ℃, and the oxidization time of present embodiment is 5 minutes, but is not limited to this, and formed oxide layer 3 ' thickness is 5 nanometers (nm)～10 nanometers.
(4) carry out step 74: utilize the Wet-type etching mode to remove this oxide layer 3 ', the incidence surface 21 of this first conductivity type substrate 2 is exposed.The solution such as present embodiment use hydrofluoric acid (HF) are as etching solution, for the SiO of this oxide layer 3 '
xMaterial has good etch effect.
(5) carry out step 75: this first conductivity type substrate 2 is carried out heat diffusion treatment, described heat diffusion treatment is first this first conductivity type substrate 2 to be inserted a high temperature furnace pipe, temperature in the boiler tube is about 750 ℃～800 ℃, and passes into a reacting gas in boiler tube, and present embodiment is N
2-POCl
3(nitrogen mixes with phosphorus oxychloride), O
2And N
2Mist, but be not limited to this, and further in these the first conductivity type substrate 2 surface deposition phosphorus (P).Then furnace tube temperature is elevated to 800 ℃～950 ℃ and kept tens of minutes, make phosphorus (P) diffuse into the top layer of this first conductivity type substrate 2, and then forming the second conductivity type emitter layer 4 of these N-shapeds at this incidence surface 21, its material is mainly phosphorus glass (PSG).
Need to prove, thermal diffusion process also can make one of this first conductivity type substrate 2 side 22 and reacting gas reaction that are connected to these incidence surface 21 peripheries, and then forming a semiconductor layer 40, the material of this semiconductor layer 40 is usually identical with this second conductivity type emitter layer 4.
(6) carry out step 76: utilize the Wet-type etching mode to remove this unnecessary semiconductor layer 40, the side 22 of this first conductivity type substrate 2 is exposed.The solution such as present embodiment use HF are as etching solution.This step is also referred to as isolated insulation (isolation) step.
(7) carry out step 77: the surface at this second conductivity type emitter layer 4 forms silicon nitride (SiN
X) anti-reflecting layer 5, for reducing sunlight reflection, promote light incident ratio.On implementing, can utilize the technology such as sputter (Sputtering) or plasma-assisted chemical vapour deposition (PECVD) to carry out.
Finished the semi-finished product of making this solar cell this moment, but it is noted that, forming anti-reflecting layer 5 is not steps necessary, so in the semi-finished product of solar cell, can not comprise this anti-reflecting layer 5 yet.
(8) carry out step 78: the semi-finished product at this solar cell form electrode 6, and electrode 6 mainly is the mode by wire mark, is formed at the upper surface of this anti-reflecting layer 5 and the lower surface of this first conductivity type substrate 2.Then above-mentioned sample is placed the sintering furnace of high temperature, the different high-temperature area of a plurality of temperature is arranged in the sintering furnace, roller in the stove drives the sintering that sample continues to advance and is subject to different high temperature, and therefore electrode 6 can adhere to securely, so namely finishes the making of solar cell.It is noted that electrode 6 forms of Fig. 2, Fig. 3 are only non-limiting for signal, also can be the aspect of other designs.
Improvement of the present invention is mainly: after the RIE etch process, in RIE equipment, proceed oxidation process at once, so this oxidation process is compatible with battery production mode originally, and its mode is simple, as long as in RIE equipment, pass into oxygen, and oxidizing temperature is identical with the temperature of original RIE processing procedure, is approximately 300 ℃～500 ℃, does not need to heat up in addition again and wastes energy and the time.In addition, because these ion damaged layers 3 are oxidized into oxide layer 3 ', therefore can utilize the etching of HF etching solution to remove, omit and use the etched step of KOH in the known processing procedure.So the present invention can save Wet-type etching one time by increasing oxidation process, because oxidation process directly carries out in RIE equipment, and oxidization time does not need oversize, therefore the oxidation process time (comprise the time that substrate moved on to etching bath and etching process) more required than the wet type etching is lacked a lot, can significantly shorten the production time, improving production efficiency, exempt simultaneously in the known method the unmanageable disappearance of the temperature when utilizing the KOH etching and concentration.Certainly, also save the expense of purchasing the KOH etching machines, and saved the occupied product space of lines of original this KOH etching machines.
Consult table 1, be the testing electrical property result of the present invention and 3 comparative examples, comparative example 1 refers to the most traditional processing procedure, does not have RIE processing procedure and Wet-type etching before diffusion process.Comparative example 2, the 3rd, another kind of known processing procedure, KOH and HF are arranged before diffusion process twice Wet-type etching altogether, speed one hurdle in the table refers to sample mobile speed of advancing in the KOH etching bath, sample moves and represents slowly that more etching process is more abundant.The V of table 1
OcRepresent open circuit voltage, J
ScRepresent short circuit current, F.F value (fill factor) represents fill factor, curve factor, and Eff. is conversion efficiency, and battery production sheet number refers in the same time (for example 1 hour), the number of batteries that the present invention and each comparative example are produced.
By table 1 result as can be known, although the speed of production of comparative example 1 is fast, battery production sheet number within the unit interval is the highest, but its short circuit current and conversion efficiency are all lower, and comparative example 2,3 is for comparative example 1, although can promote short circuit current and conversion efficiency, speed of production is too slow, is unfavorable for volume production.Review the present invention, for comparative example 1, short circuit current of the present invention and conversion efficiency promote respectively 0.59mA/cm
2And 0.2%, this is for quite significantly promoting, although production capacity of the present invention descends slightly, but this range of decrease is small, and production capacity of the present invention is still highlyer with respect to comparative example 2,3, and speed of production of the present invention has been fit to volume production, so the present invention averages out between battery efficiency and production efficiency.
Table 1
In sum, by oxidation process plasma breakable layer 3 is oxidized into this oxide layer 3 ', making the present invention only need a Wet-type etching before heat diffusion treatment is removable this oxide layer 3 ', significantly reduce the processing procedure time, promote production capacity, can take into account the feasibility of volume production and the conversion efficiency of solar cell.
Claims (9)
1. the manufacture method of a solar cell comprises: steps A: utilize first conductivity type substrate of dry-etching mode etching, make an incidence surface of this first conductivity type substrate become the shape that just rises and falls, and this incidence surface also forms a plasma breakable layer; It is characterized in that the manufacture method of this solar cell also comprises the following step:
Step B: these ion damaged layers of oxidation make these ion damaged layers be transformed into an oxide layer;
Step C: utilize the Wet-type etching mode to remove this oxide layer;
Step D: this first conductivity type substrate is carried out heat diffusion treatment, make the incidence surface of this first conductivity type substrate form second a conductivity type emitter layer, to finish the semi-finished product of making this solar cell;
Step e: the semi-finished product at this solar cell form electrode.
2. the manufacture method of solar cell according to claim 1 is characterized in that, the oxidizing temperature of step B is 300 ℃～500 ℃.
3. the manufacture method of solar cell according to claim 1 and 2 is characterized in that, the thickness of this oxide layer is 5 nanometers～10 nanometers.
4. the manufacture method of solar cell according to claim 3 is characterized in that, the oxidization time of step B is 1 minute～25 minutes.
5. the manufacture method of solar cell according to claim 1 and 2 is characterized in that, the dry-etching of steps A utilizes the reactive ion etch mode.
6. the manufacture method of solar cell according to claim 5 is characterized in that, the material of this oxide layer comprises the oxide of silicon, and the etching solution of step C Wet-type etching is hydrofluoric acid solution.
7. the manufacture method of solar cell according to claim 1, it is characterized in that, also comprise one and be positioned at step D step F afterwards, form an anti-reflecting layer at this second conductivity type emitter layer, step e forms described electrode on the surface of this anti-reflecting layer and the surface of this first conductivity type substrate.
8. the manufacture method of solar cell according to claim 1 is characterized in that, the heat diffusion treatment of step D also can make a side of this first conductivity type substrate form a semiconductor layer, then recycles the Wet-type etching mode and removes this semiconductor layer.
9. the manufacture method of solar cell according to claim 8 is characterized in that, is hydrofluoric acid solution for the etching solution that removes this semiconductor layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946378A (en) * | 2016-10-12 | 2018-04-20 | 英属开曼群岛商精曜有限公司 | Solar battery structure |
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