CN102956742B - Manufacturing method of solar cell - Google Patents
Manufacturing method of solar cell Download PDFInfo
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- CN102956742B CN102956742B CN201110244060.4A CN201110244060A CN102956742B CN 102956742 B CN102956742 B CN 102956742B CN 201110244060 A CN201110244060 A CN 201110244060A CN 102956742 B CN102956742 B CN 102956742B
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- solar cell
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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 after surface roughening with reactive ion etch (RIE) technology.
Background technology
The processing procedure of general silicon wafer solar cell, is the silicon substrate of one piece of p-type is carried out thermal diffusion (thermal diffusion) process, makes this substrate surface form the emitter layer of a N-shaped, and then form p-n junction.But research finds when the incidence surface of this battery is rough surface concavo-convex up and down, can reduce light reflection, promote the ratio of light to inside battery, and promote conversion efficiency.Therefore having a kind of improvement processing procedure at present, is before diffusion process, utilize reactive ion etch (Reactive Ion Etching is called for short RIE) mode, etching substrate surface and form rough surface.
Consult Fig. 1, although RIE processing procedure energy etching substrates 11 and reach the demand of substrate 11 concave-convex surface, but therefore the charged particle (plasma) in this processing procedure also can react with substrate 11 material, substrate 11 surface is made to form first-class ion damaged layer 12, the existence of these ion damaged layers 12 will increase the Percentage bound again (Recombination) of charge carrier, thus the photoelectric conversion efficiency of solar cell can be reduced, so after RIE processing procedure, these ion damaged layers 12 must be removed again by Wet-type etching mode, material due to 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 with hydrofluoric acid (HF) etching solution etching SiO respectively
x, and with potassium hydroxide (KOH) etching solution etching Si.After these ion damaged layers 12 remove, then carry out heat diffusion treatment to form p-n junction.
And the shortcoming of above-mentioned processing procedure is: when using KOH to etch Si, due to Si itself characteristic caused by, etch time temperature and KOH concentration all to precisely control, the Si of predetermined thickness could be removed, but about the control between the thickness of Si and etch temperature, concentration, and be not easy to control.In addition, when carrying out Wet-type etching, first substrate 11 to be moved on in the etching bath being full of KOH solution and etch, then again substrate 11 is moved on to the etching bath etching that another is full of HF solution, need to expend time in owing to substrate 11 to be moved on to etching bath, above-mentioned processing procedure carries out twice Wet-type etching, so the time spent by moving substrate 11 will increase to twice in two different etching baths still more, therefore its processing time is long, production efficiency is low, is unfavorable for industrial production.And the above-mentioned etching for carrying out KOH and HF, two etching machines need be adopted just to carry out, and the cost of board equipment like this can significantly increase, and will cause the problem of cost control in volume production, and two equipment also produce the problem occupying 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 time, and the manufacture method of the solar cell of battery conversion efficiency and volume production demand can be taken into account.Thus the cost of equipment purchase can be reduced and avoid occupying the problem in too much plant area's production line space.
The manufacture method of solar cell of the present invention, comprises:
Steps A: utilize dry-etching mode to etch one first conduction type substrate, make an incidence surface of this first conduction type substrate become the shape that just rises and falls, and this incidence surface also forms a plasma breakable layer;
Step B: be oxidized these ion damaged layers, makes these ion damaged layer changes become an oxide layer;
Step C: utilize Wet-type etching mode to remove this oxide layer;
Step D: carry out heat diffusion treatment to this first conduction type substrate, makes the incidence surface of this first conduction type substrate form a second conductivity type emitter layer, to complete the semi-finished product making this solar cell; And
Step e: form electrode on the semi-finished product of this solar cell.
Method of the present invention, the oxidizing temperature of step B is 300 DEG C ~ 500 DEG C.
Method of the present invention, the thickness of this oxide layer is 5 nanometer ~ 10 nanometers.
Method of the present invention, the oxidization time of step B is 1 minute ~ 25 minutes.
Method of the present invention, the dry-etching of steps A utilizes 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 comprise one be positioned at step D after step F, on this second conductivity type emitter layer formed an anti-reflecting layer, step e forms described electrode on the surface of the surface of this anti-reflecting layer and this first conduction type substrate.
Method of the present invention, the heat diffusion treatment of step D also can make this first conduction type substrate side form a semiconductor layer, then recycles Wet-type etching mode and removes this semiconductor layer.
Method of the present invention is hydrofluoric acid solution for removing the etching solution of this semiconductor layer.
The principal carrier of described first conduction type substrate and this second conductivity type emitter layer must not limit, as long as can form p-n junction, therefore when this first conduction type substrate is p-type semiconductor, this second conductivity type emitter layer is n-type semiconductor; When this first conduction type substrate is n-type semiconductor, this second conductivity type emitter layer is p-type semiconductor.
The described oxidizing temperature for being oxidized these ion damaged layers is 300 DEG C ~ 500 DEG C, and oxidization time is 1 ~ 25 minute, makes formed oxidated layer thickness be 5 nanometers (nm) ~ 10 nanometer.Wherein, oxidizing temperature must limit lower limit, is because when temperature is too low, because temperature is not enough, reactant gas molecules cannot be made to produce enough mobile kinetic energy, this reacting gas will be caused fully to react with these ion damaged layers and to be oxidized; And oxidizing temperature just can reach fully oxidized effect in 500 DEG C, do not need again temperature to be raised, because improve temperature more also just cause energy waste.In addition, due to this oxidation process be continue this steps A dry-etching and carry out, and two steps are carried out in same vacuum cavity, and cavity temperature roughly all maintains 300 DEG C ~ 500 DEG C, therefore oxidizing temperature must additionally not change again, quite convenient in making.
The present invention is for the restriction of oxidization time, also be to make these ion damaged layers fully can react oxidation, it should be noted that, the oxidation rate of these ion damaged layers along with the increase of oxidization time will be slack-off gradually, therefore can play the highest oxidation efficiency in oxidization time in the early stage, oxidization time does not need oversize.
Beneficial effect of the present invention is: by carrying out oxidation process after RIE processing procedure, plasma breakable layer is oxidized to oxide layer, make the present invention can omit KOH etching step before heat diffusion treatment, and only need Wet-type etching once and this oxide layer removable, significantly reduce processing time, promote production capacity, the feasibility of volume production and the conversion efficiency of solar cell can be taken into account.
Accompanying drawing explanation
Fig. 1 is a kind of schematic diagram of part-structure of known solar cells;
Fig. 2 is a schematic diagram, shows the solar cell manufactured by preferred embodiment of the manufacture method of solar cell of the present invention;
Fig. 3 is the schematic diagram of this preferred embodiment each step when carrying out;
Fig. 4 is the steps flow chart calcspar of this preferred embodiment.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Consult Fig. 2, the preferred embodiment of manufacture method of the present invention, for the manufacture of a solar cell, described solar cell comprises one first conduction type substrate 2, the second conductivity type emitter layer 4, be positioned on an incidence surface 21 of this first conduction type substrate 2 and is positioned at the electrode 6 that anti-reflecting layer 5 on this second conductivity type emitter layer 4 and two lay respectively at the lower surface of this first conduction type substrate 2 and the surface of anti-reflecting layer 5, described electrode 6 for delivery of electrical energy that battery is produced 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 conduction type substrate 2, the present embodiment is p-type semiconductor silicon (Si) substrate.
(2) carry out step 72: utilize dry-etching mode to etch the surface of this first conduction type substrate 2, the present embodiment uses 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 DEG C ~ 500 DEG C, and passes into SF
6, Cl
2and O
2mist, as reacting gas, makes the incidence surface 21 of the first conduction type substrate 2 form the shape that just rises and falls, namely forms concavo-convex coarse micro-structural (Texturing).And because the surface of this first conduction type substrate 2 can produce with plasma react, therefore this incidence surface 21 also can form a plasma breakable layer 3, these ion damaged layer 3 materials are mainly the oxide (SiO of silicon (Si) and silicon
x).
(3) carry out step 73: by aforementioned SF
6and Cl
2air flow source close, in vacuum cavity, only pass into O
2gas, O
2be provoked in cavity as oxygen plasma and continue to react with these ion damaged layers 3, and then be oxidized by these ion damaged layers 3 and be transformed into an oxide layer 3 ', its material is mainly SiO
x.In this oxidizing process, this cavity temperature i.e. oxidizing temperature are about 300 DEG C ~ 500 DEG C, and the oxidization time of the present embodiment is 5 minutes, but is not limited thereto, and the oxide layer 3 ' thickness formed is 5 nanometers (nm) ~ 10 nanometer.
(4) carry out step 74: utilize Wet-type etching mode to remove this oxide layer 3 ', the incidence surface 21 of this first conduction type substrate 2 is exposed.The present embodiment uses the solution such as hydrofluoric acid (HF) as etching solution, for the SiO of this oxide layer 3 '
xmaterial has good etch effect.
(5) carry out step 75: heat diffusion treatment is carried out to this first conduction type substrate 2, described heat diffusion treatment first this first conduction type substrate 2 is inserted a high temperature furnace pipe, temperature in boiler tube is about 750 DEG C ~ 800 DEG C, and in boiler tube, pass into a reacting gas, and the present embodiment is N
2-POCl
3(nitrogen mixes with phosphorus oxychloride), O
2and N
2mist, but to be not limited thereto, and further in this first conduction type substrate 2 surface deposition phosphorus (P).Then furnace tube temperature be elevated to 800 DEG C ~ 950 DEG C and maintain several tens minutes, phosphorus (P) is made to diffuse into the top layer of this first conduction type substrate 2, and then on this incidence surface 21, forming the second conductivity type emitter layer 4 of this N-shaped, its material is mainly phosphorus glass (PSG).
It should be noted that, thermal diffusion process also can make this first conduction type substrate 2 side 22 being connected to this incidence surface 21 periphery react with reacting gas, 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 Wet-type etching mode to remove this unnecessary semiconductor layer 40, the side 22 of this first conduction type substrate 2 is exposed.The present embodiment uses the solution such as HF as etching solution.This step is also referred to as isolated insulation (isolation) step.
(7) carry out step 77: form silicon nitride (SiN on the surface of this second conductivity type emitter layer 4
x) anti-reflecting layer 5, for reducing sunlight reflection, promote light ratio.In enforcement, the technology such as sputter (Sputtering) or plasma-assisted chemical vapour deposition (PECVD) can be utilized to carry out.
Now complete and made the semi-finished product of this solar cell, but it is noted that, formed anti-reflecting layer 5 and optional step, in the semi-finished product of therefore solar cell, also can not comprise this anti-reflecting layer 5.
(8) carry out step 78: on the semi-finished product of this solar cell, form electrode 6, electrode 6, mainly by the mode of wire mark, is formed at the upper surface of this anti-reflecting layer 5 and the lower surface of this first conduction type substrate 2.Then above-mentioned sample is placed in the sintering furnace of high temperature, the high-temperature area that multiple temperature is different is had in sintering furnace, roller in stove drives sample to continue to advance and is subject to the sintering of different high temperature, and therefore electrode 6 can adhere to securely, so namely completes the making of solar cell.It is noted that, electrode 6 form of Fig. 2, Fig. 3 is only signal and non-limiting, also can be the aspect of other designs.
Improvement of the present invention is mainly: after 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 pass into oxygen in RIE equipment, and oxidizing temperature is identical with the temperature of original RIE processing procedure, be approximately 300 DEG C ~ 500 DEG C, do not need heat up in addition again and waste energy and the time.In addition, because these ion damaged layers 3 are oxidized into oxide layer 3 ', HF etching solution therefore can be utilized to etch and to remove, omit the step using KOH to etch in known processing procedure.So the present invention can save a Wet-type etching by increasing oxidation process, because oxidation process directly carries out in RIE equipment, and oxidization time does not need oversize, therefore oxidation process is fewer than the time (comprising time substrate being moved on to etching bath and etching process) needed for Wet-type etching a lot, can significantly shorten production time, improving production efficiency, exempt in known method, the unmanageable disappearance of temperature and concentration when utilizing KOH to etch simultaneously.Certainly, also save the expense purchasing KOH etching machines, and save this product space of lines occupied by KOH etching machines original.
Consult table 1, be the electrical test results 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 2,3 is another kind of known processing procedures, have KOH and HF before the diffusion process Wet-type etching of twice altogether, and speed one hurdle in table refers to sample mobile speed of advancing in KOH etching bath, and sample moves and represents that etching process is more abundant more slowly.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 same time (such as 1 hour), the number of batteries that the present invention and each comparative example are produced.
As seen from the results in Table 1, 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 0.59mA/cm respectively
2and 0.2%, this is for quite significantly to promote, although production capacity of the present invention declines slightly, but this range of decrease is small, and production capacity of the present invention is still higher relative to comparative example 2,3, speed of production of the present invention is applicable to volume production, and therefore 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 ', the present invention is made only to need a Wet-type etching and this oxide layer 3 ' removable before heat diffusion treatment, significantly reduce processing time, promote production capacity, the feasibility of volume production and the conversion efficiency of solar cell can be taken into account.
Claims (9)
1. a manufacture method for solar cell, comprises:
Utilize dry-etching mode to etch first conduction type substrate, make this first conduction type substrate incidence surface 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:
Be oxidized these ion damaged layers to form an oxide layer;
Wet-type etching mode is utilized to remove this oxide layer;
Heat diffusion treatment is carried out to this first conduction type substrate, to form a second conductivity type emitter layer at this incidence surface; And
This first conduction type substrate forms an electrode.
2. the manufacture method of solar cell according to claim 1, is characterized in that, the oxidizing temperature being oxidized these ion damaged layers is 300 DEG C ~ 500 DEG C.
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 nanometer ~ 10 nanometers.
4. the manufacture method of solar cell according to claim 3, is characterized in that, the oxidization time being oxidized these ion damaged layers is 1 minute ~ 25 minutes.
5. the manufacture method of solar cell according to claim 1 and 2, is characterized in that, dry-etching utilizes 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 Wet-type etching is hydrofluoric acid solution.
7. the manufacture method of solar cell according to claim 1, is characterized in that, is also included on this second conductivity type emitter layer and forms an anti-reflecting layer, then form described electrode.
8. the manufacture method of solar cell according to claim 1, is characterized in that, this heat diffusion treatment also can make this first conduction type substrate side form a semiconductor layer, then removes this semiconductor layer in Wet-type etching mode again.
9. the manufacture method of solar cell according to claim 8, is characterized in that, is hydrofluoric acid solution for removing the etching solution of this semiconductor layer.
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| CN201110244060.4A CN102956742B (en) | 2011-08-24 | 2011-08-24 | Manufacturing method of solar cell |
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| CN201110244060.4A CN102956742B (en) | 2011-08-24 | 2011-08-24 | Manufacturing method of solar cell |
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| CN102956742B true CN102956742B (en) | 2015-04-22 |
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| 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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| JP4339990B2 (en) * | 2000-08-31 | 2009-10-07 | 京セラ株式会社 | Surface roughening method of silicon substrate |
| KR100990108B1 (en) * | 2010-04-14 | 2010-10-29 | 엘지전자 주식회사 | Solar cell and method for manufacturing the same |
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| CN101478013A (en) * | 2008-12-30 | 2009-07-08 | 无锡尚德太阳能电力有限公司 | Method for producing solar cell silicon wafer suede by reactive ion etching and solar cell produced thereby |
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