CN101764179A - Manufacture method of selective front surface field N-type solar cell - Google Patents
Manufacture method of selective front surface field N-type solar cell Download PDFInfo
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a manufacture method of a selective front surface field N-type solar cell, which is characterized in that a back surface p-n junction is formed by utilizing an aluminum-silicon alloying process and a high-temperature boron diffusion process, a front surface lightly doped N-type layer is formed by high-temperature phosphorous diffusion, a front surface local heavily doped N-type region is formed by laser doping, and a front electrode is manufactured on the heavily doped N-type region by utilizing a chemical plating method or an electroplating method. Compared with the traditional manufacture process, the invention has the advantages of simple process and low cost and does not need secondary contraposition.
Description
Technical field
The invention belongs to the solar energy power generating field, be specifically related to a kind of manufacture method of selective front surface field N-type solar cell.
Background technology
Solar cell is a kind of semiconductor device that utilizes photovoltaic effect solar energy directly to be converted to electric energy.On structure, solar cell generally is made up of Semiconductor substrate, the p-n junction that is positioned at semiconductor substrate surface, height knot, deielectric-coating and metal electrode.
According to the difference of substrate conduction type, can be divided into two kinds in P type and N type solar cell to solar cell.P type solar cell technical maturity has occupied the leading position in current solar cell market.But, P type solar cell boron, too high oxygen level, boron oxygen tangible performance degradation occurs to can cause P type solar cell under action of ultraviolet light.This makes a lot of research institutions and manufacturing enterprise transfer to sight on the N type solar cell.Because N type crystalline silicon boron content is few, thus also not obvious by boron-oxygen to the photo attenuation phenomenon that is caused.In addition, because N type crystalline silicon is better than P type crystalline silicon to the tolerance of transition metal such as iron, so generally speaking, N type crystalline silicon has higher minority carrier life time.This is highly beneficial for making efficient solar battery.
According to the residing position of p-n junction, emitter N type solar cell and emitters on back side N type solar cell two classes before N type solar cell can be divided into again.Preceding emitter N type solar cell is generally made p-n junction by the method for carrying out the high temperature boron diffusion at N type semiconductor substrate front surface.This battery structure is simple, and with conventional P type solar cell manufacture craft basically identical, thereby be easy to realize industrialization.But the boron atom that is in the solar cell front surface still can be right with the oxygen formation boron oxygen in the substrate, can cause the solar cell performance to occur descending equally under the UV-irradiation for a long time.
Then there be not the photo attenuation phenomenon of boron oxygen to causing substantially in emitters on back side N type solar cell.Emitters on back side N type solar cell is made p-n junction by the method for carrying out the high temperature boron diffusion on N type semiconductor substrate back of the body surface.Because ultraviolet light just is absorbed totally in the very shallow zone of solar cell front surface, ultraviolet light is difficult to incide solar cell back of the body surface, and back of the body surface boron oxygen is to causing solar cell tangible performance degradation to occur lacking under the situation of ultraviolet irradiation.
Except boron emitters on back side N type solar cell, aluminized emitter N-type solar battery also is a kind of promising N type solar battery structure.The structure of aluminized emitter N-type solar battery is the same substantially with boron emitter N type solar cell, and just its back of the body surface p-n knot is to form by the alloying process that N type crystalline silicon substrate and aluminium electrode at high temperature take place.Aluminized emitter N-type solar battery is because boron content is few, so do not exist equally by the photo attenuation phenomenon of boron oxygen to being caused.
Though there is not the problem of photo attenuation, the emitters on back side structure has been brought the other shortcoming.Because most of sunlights are absorbed at the solar cell front surface, the photo-generated carrier of its generation must be moved to solar cell back of the body surface p-n knot just can be collected utilization.In transition process, photo-generated carrier is easy to be captured by the defective in solar cell front surface or the substrate, thereby influences the performance of solar cell.Therefore, the efficient that improve emitters on back side N type solar cell just must reduce photo-generated carrier compound in solar cell front surface and substrate body.
Reduce the front surface doping content and can effectively reduce photo-generated carrier compound at the solar cell front surface, but low excessively surface doping concentration is unfavorable for that forming good ohmic between the electrode and substrate before the metal contacts.The selective front surface field N-type solar cell structure has solved above-mentioned contradiction well.As shown in Figure 1, near the heavy doping N type zone the front electrodes of solar cells has guaranteed that metal electrode and Semiconductor substrate form good ohmic and contact; And the solar cell front surface all is light dope N type layer except that the electrode near zone, and this helps reducing the average doping content of solar cell front surface, thereby reduces photo-generated carrier compound at front surface.
Because need carrying out local to front surface, selective front surface field N-type solar cell mixes, so the common relatively solar cell of manufacture craft is wanted complexity.As shown in Figure 2, traditional manufacture method is to carry out heavy doping in the local location fluting and the cross-notching zone of deielectric-coating earlier, removes deielectric-coating subsequently and whole front surface is carried out light dope, so just can obtain selective front surface field.Laboratory photoetching method commonly used is slotted to deielectric-coating, but photoetching method is with high costs, complex process, and is not suitable for using in the industrial production.
Chinese patent CN 101101936A proposes a kind of employing silk screen printing corrosive agent and slots, and carries out the method that the diffusion of two steps obtains selective emitter.This method has low, the advantage of simple technology of cost, also is applicable to the making of selective front surface field simultaneously.But, adopt this method often when electrode is made in follow-up silk screen printing, to encounter difficulties.Because preceding electrode must be followed heavy doping N type area coincidence, this aligning accuracy to silk screen printing requires very high.In order to overcome above-mentioned contraposition problem, can be heavy doping N type zone broadening, but so improve the draw doping content of solar cell front surface again, increased photo-generated carrier compound at front surface.
Summary of the invention
The purpose of this invention is to provide a kind of selective front surface field N-type solar cell manufacture method of suitable suitability for industrialized production, it is simple that this method possesses technology, with low cost and need not characteristics such as contraposition.
The manufacture method of a kind of selective front surface field N-type solar cell provided by the invention, it is characterized in that, utilize alusil alloy process or high temperature boron diffusion process to form back of the body surface p-n knot, high temperature phosphorous diffuses to form front surface light dope N type layer, laser doping forms front surface local heavy doping N type zone, and electrode before making on above-mentioned heavy doping N type zone of chemical plating or electro-plating method.
According to the type (boron emitter or aluminium emitter) of the back of the body surface emitting utmost point, above-mentioned manufacture method can be subdivided into two similar technical schemes.
First technical scheme is to utilize the alusil alloy process to form back of the body surface p-n knot, high temperature phosphorous diffuses to form front surface light dope N type layer, laser doping forms front surface local heavy doping N type zone, and electrode before making on above-mentioned heavy doping N type zone of chemical plating or electro-plating method, specifically may further comprise the steps:
(a) the N type semiconductor substrate is carried out surface-texturing and carries out chemical cleaning
The purpose of surface-texturing is to increase the order of reflection of sunlight at solar battery surface, thereby increases the absorption of light.For monocrystalline substrate, generally adopt aqueous slkali (as rare sodium hydroxide solution) to form the matte of Pyramid at substrate surface; And, generally adopt the matte of the mixed solution of hydrofluoric acid, nitric acid and water at substrate surface formation pit shape for the polysilicon substrate.
The purpose of chemical cleaning is to remove the impurity of substrate surface, for follow-up diffusion technology is prepared.The general hydrochloric acid and the hydrofluoric acid of dilution of adopting cleans.
(b) front surface light dope N type layer is made in the high temperature phosphorous diffusion
Utilize high temperature phosphorous to diffuse to form one deck light dope N type layer.This light dope N type layer is to adopt phosphorus oxychloride as the phosphorus source, spreads to obtain under 800～1000 ℃ temperature.In order to reduce the average doping content of front surface, the square resistance of this light dope N type layer at 45 Ω/ between 120 Ω/.
(c) prepare deielectric-coating at N type semiconductor substrate front surface
The effect of deielectric-coating has three: the one, as antireflective coating, increase the incident of sunlight; The 2nd, play the surface passivation effect, the minimizing photo-generated carrier is compound battery surface; The 3rd, as the mask of subsequent chemistry plating, plating, avoid the place beyond electrode zone to plate metal.
Deielectric-coating of the present invention is meant mono-layer oxidized silicon, silicon nitride, amorphous silicon or pellumina, or the stack membrane of any above-mentioned monofilm composition.
(d-1) at N type semiconductor substrate back of the body surface preparation aluminium electrode
For aluminized emitter N-type solar battery, the aluminium electrode also carries out P type to the N type semiconductor substrate as dopant and mixes, thereby form p-n junction except collected current in sintering process.
Aluminium electrode of the present invention can adopt silk screen printing, sputter or evaporation coating method to be prepared.This aluminium electrode covers the entire area of N type semiconductor substrate surface or the most of area except that the edge.
(d-2) thus high temperature sintering forms the back of the body that surperficial P type layer obtains p-n junction
For aluminized emitter N-type solar battery, when sintering temperature is higher than 575 ℃ of al-si eutectic point temperature, the aluminium silicon interface will form the alusil alloy layer that melts altogether.Therefore under 575～1000 ℃ of environment that promptly are not less than the al-si eutectic temperature, solar cell is heat-treated.In the cooling procedure of sintering, the silicon recrystallization of fusion is also separated out the aluminium that exceeds its solid solubility, but still has micro-aluminium atom to remain in the recrystallization zone of silicon substrate.This recrystallization zone is the P-type conduction type, constitutes p-n junction with N type substrate.
(e) in N type semiconductor substrate back of the body surface preparation silver electrode
Adopt printing, sputter or evaporation coating method to make silver electrode on back of the body surface.
(f) in N type semiconductor substrate front surface phosphors coating source
The phosphors coating source mainly is to provide impurity source for follow-up laser doping.Phosphors coating of the present invention source step realizes by spraying, spin coating or silk screen printing, phosphorosilicate glass layer or other phosphorus containg substances that described phosphorus source forms when being meant phosphoric acid, phosphoric acid-alcohol mixed solution, high temperature phosphorous diffusion.
(g) carry out laser doping at N type semiconductor substrate front surface and form local heavy doping N type zone
Laser doping is in order to form local heavy doping N type zone at the substrate front surface.Adopt laser scanning to scribble the substrate surface in phosphorus source in the manufacturing process, the high temperature that laser produces makes the backing material fusion this zone in and mixes the heavily doped N type of formation zone with the phosphorus source.Because the effect in heavy doping N type zone is and metal electrode forms ohmic contact, so doping content that should the zone is wanted enough height, the present invention requires its square resistance to be not more than 45 Ω/; In addition, the laser doping zone is consistent with the front electrodes of solar cells shape of design, generally is pectination and is distributed in the solar cell front surface.
(h) make on heavy doping N type zone of chemical plating or electro-plating method before electrode
Electrode is with silver, copper, nickel, tin or contains the alloy composition of above-mentioned element before of the present invention, and this preceding electrode is positioned at the groove that laser ablation produces, and is covered on the local heavy doping N type layer.The resistivity of silver, copper is low, helps obtaining low electrode body resistance; The contact potential of nickel and silicon is low, helps forming good Ohmic contact; And the good welding performance of tin helps improving the adhesion between solar cell and the interconnecting strip.A kind of technical scheme that the present invention proposes is to adopt chemical plating method in the thin nickel electrode of local heavy doping N type layer plating one deck earlier, uses electro-plating method silver-plated or copper on nickel electrode again.Another kind of technical scheme is directly to adopt electro-plating method nickel plating, re-plating copper or silver.If select for use copper as electrode, also need on copper, electroplate one deck tin or silver, can improve the solderability of electrode like this.
Second technical scheme of the present invention is to utilize high temperature boron diffusion process to form back of the body surface p-n knot, high temperature phosphorous diffuses to form the front surface lightly-doped layer, laser doping forms front surface local heavy doping N type zone, and electrode before making on above-mentioned heavy doping N type zone of chemical plating or electro-plating method, specifically may further comprise the steps:
(a) the N type semiconductor substrate is carried out surface-texturing and carries out chemical cleaning;
(b) front surface light dope N type layer is made in the high temperature phosphorous diffusion;
(c) prepare deielectric-coating at N type semiconductor substrate front surface;
(d) thus the high temperature boron diffusion forms the back of the body that surperficial P type layer obtains p-n junction;
(e) carry on the back surface preparation silver electrode and aluminium electrode and carry out high temperature sintering at the N type semiconductor substrate;
(f) in N type semiconductor substrate front surface phosphors coating source;
(g) carry out laser doping at N type semiconductor substrate front surface and form local heavy doping N type zone;
(h) electrode before usefulness chemical plating, electro-plating method are made on heavy doping N type zone.
Second technical scheme and first technical scheme basically identical, just (d) step is different.Its essence is with high temperature boron diffusion process replaces the alusil alloy process to form p-n junction.High temperature boron diffusion process is meant and adopts Boron tribromide as the boron source, under 800～1000 ℃ temperature substrate carried out the process that the P type mixes.
It is simple that selective front surface field N-type solar cell manufacture method provided by the invention has technology, is fit to suitability for industrialized production, with low cost and need not characteristics such as secondary contraposition.
Description of drawings
Fig. 1 is the selective front surface field N-type solar cell structural representation;
Fig. 2 is the traditional fabrication method of selective front surface field N-type solar cell;
Fig. 3 is one of selective front surface field N-type solar cell manufacture method provided by the invention;
Fig. 4 is two of a selective front surface field N-type solar cell manufacture method provided by the invention;
In Fig. 1～4,1, the N type semiconductor substrate, 2, the heavy doping n type semiconductor layer, 3, deielectric-coating, 4, back of the body surfaces of aluminum electrode, 5, carry on the back surperficial silver electrode, 6, electrode before the metal, 7, p type semiconductor layer, 8, the phosphorus source, 9, the light dope n type semiconductor layer.
Embodiment
Fig. 3 is first technical scheme of selective front surface field N-type solar cell manufacture method provided by the invention, specifically may further comprise the steps:
(a) the N type semiconductor substrate is carried out surface-texturing and carries out chemical cleaning
For the n type single crystal silicon substrate, adopt rare NaOH or potassium hydroxide solution to make the light trapping structure of Pyramid at substrate surface; For N type polysilicon substrate, adopt nitric acid, hydrofluoric acid mixed solution to make the light trapping structure of pit shape at substrate surface.Subsequently, adopt the hydrochloric acid and the hydrofluoric acid of dilution that substrate is cleaned respectively.
(b) high temperature phosphorous diffuses to form front surface light dope N type layer
Adopt phosphorus oxychloride as doped source, under 800-1000 ℃ of (as 850 ℃) temperature, Semiconductor substrate spread and obtain light dope N type layer.The square resistance of this N type layer is controlled at 45 Ω/ to 120 Ω/, as 90 Ω/.
(c) prepare deielectric-coating at N type semiconductor substrate front surface
Adopt the silicon oxide film of hot oxygen oxidation, again with the silicon nitride film of plasma enhanced chemical vapor deposition method at the about 70nm of substrate front surface deposition at the about 10nm of substrate surface generation one deck.
(d-1) at N type semiconductor substrate back of the body surface preparation aluminium electrode
In the about 25 μ m of substrate back of the body surface screen-printed thick aluminum slurry and oven dry.
(d-2) thus high temperature sintering forms the back of the body that surperficial P type layer obtains p-n junction
Adopt chain-type sintering furnace that solar cell is carried out high temperature sintering, maximum temperature is got 575～1000 ℃, as 850 ℃.
(e) in N type semiconductor substrate back of the body surface preparation silver electrode
The method that adopts printing, sputter or evaporation is at N type semiconductor substrate back of the body surface preparation argent electrode.
(f) in N type semiconductor substrate front surface phosphors coating source
Adopt spin coating method to apply one deck phosphoric acid-alcoholic solution at the silicon chip front surface.
(g) carry out laser doping at N type semiconductor substrate front surface and form local heavy doping N type zone
Scan at the substrate front surface with laser, the square resistance in laser doping zone is controlled at 45 Ω/below the, as 20 Ω/.
(h) make on heavy doping N type zone of chemical plating or electro-plating method before electrode
Utilize chemical plating nickel coating electrode on heavy doping N type zone, adopt electro-plating method silver-plated on nickel electrode again.
Fig. 4 is second technical scheme of selective front surface field N-type solar cell manufacture method provided by the invention, specifically may further comprise the steps:
(a) the N type semiconductor substrate is carried out surface-texturing and carries out chemical cleaning;
(b) high temperature phosphorous diffuses to form front surface light dope N type layer;
(c) prepare deielectric-coating at N type semiconductor substrate front surface;
(d) high temperature boron diffusion process forms the surperficial P type layer of the back of the body, thereby obtains carrying on the back surface p-n knot (adopt Boron tribromide as doped source, carry out the diffusion of P type under 800-1000 ℃ temperature);
(e) prepare silver electrode, aluminium electrode in N type semiconductor substrate back of the body surface screen-printed, and carry out high temperature sintering;
(f) in N type semiconductor substrate front surface phosphors coating source;
(g) carry out laser doping at the substrate front surface and form local heavy doping N type zone;
(h) electrode before usefulness chemical plating, electro-plating method are made on heavy doping N type zone.
Present embodiment is except that step (d), and other step is consistent with embodiment 1.
In a word, the present invention has exemplified above-mentioned preferred implementation, but should illustrate, those skilled in the art can carry out various variations and remodeling according to the kind of each parameter range disclosed by the invention and each parameter, deielectric-coating can be mono-layer oxidized silicon, silicon nitride, amorphous silicon or pellumina as described in the present invention, or the stack membrane of any above-mentioned monofilm composition; Aluminium electrode of the present invention can adopt silk screen printing, sputter or evaporation coating method to be prepared; Make silver electrode on back of the body surface and can adopt printing, sputter or evaporation coating method; Phosphors coating of the present invention source step realizes by spraying, spin coating or silk screen printing, phosphorosilicate glass layer or other phosphorus containg substances that described phosphorus source forms when being meant phosphoric acid, phosphoric acid-alcohol mixed solution, high temperature phosphorous diffusion.Therefore, unless such variation and remodeling have departed from scope of the present invention, otherwise all should be included in protection scope of the present invention.
Claims (10)
1. the manufacture method of a selective front surface field N-type solar cell, it is characterized in that, utilize alusil alloy process or high temperature boron diffusion process to form back of the body surface p-n knot, high temperature phosphorous diffuses to form front surface light dope N type layer, laser doping forms front surface local heavy doping N type zone, and electrode before making on above-mentioned heavy doping N type zone of chemical plating or electro-plating method, specifically may further comprise the steps:
(a) the N type semiconductor substrate is carried out surface-texturing and carries out chemical cleaning;
(b) front surface light dope N type layer is made in the high temperature phosphorous diffusion;
(c) prepare deielectric-coating at N type semiconductor substrate front surface;
(d) make p-n junction on N type semiconductor substrate back of the body surface;
(e) make silver electrode and aluminium electrode on N type semiconductor substrate back of the body surface;
(f) in N type semiconductor substrate front surface phosphors coating source;
(g) carry out laser doping at N type semiconductor substrate front surface and form local heavy doping N type zone;
(h) make on heavy doping N type zone of chemical plating or electro-plating method before electrode.
2. manufacture method according to claim 1, it is characterized in that, the described high temperature phosphorous diffusion of step (b) is meant adopts phosphorus oxychloride as the phosphorus source, under 800～1000 ℃ temperature the N type semiconductor substrate is carried out the N type and mix, the square resistance of described light dope N type layer is between 45 Ω/ to 120 Ω/.
3. manufacture method according to claim 1 is characterized in that, the described p-n junction making of step (d) is meant and utilizes alusil alloy process or high temperature boron diffusion process to make p-n junction.
4. manufacture method according to claim 3 is characterized in that, the described method of utilizing the alusil alloy process to form p-n junction may further comprise the steps:
(a) adopt the method for silk screen printing, sputter or evaporation on the N type semiconductor substrate, to cover the layer of aluminum electrode;
(b) under 575～1000 ℃ of environment that promptly are not less than the al-si eutectic temperature, solar cell is heat-treated.
5. manufacture method according to claim 3, it is characterized in that, the described method of utilizing high temperature boron diffusion process to form p-n junction is meant and adopts Boron tribromide as the boron source, under 800～1000 ℃ temperature the N type semiconductor substrate carried out the process that the P type mixes.
6. manufacture method according to claim 1, it is characterized in that, the described phosphors coating of step (f) source adopts spraying, spin coating or screen printing mode to be achieved, the phosphorosilicate glass layer that described phosphorus source forms when being meant phosphoric acid, phosphoric acid-alcohol mixed solution or high temperature phosphorous diffusion.
7. manufacture method according to claim 1 is characterized in that, the described laser doping of step (g) is meant adopts laser ablation N type semiconductor substrate, mixes the backing material fusion in the ablated area and with the phosphorus source to form local heavy doping N type zone.
8. manufacture method according to claim 7 is characterized in that, described local heavy doping N type zone is pectination and is distributed in the solar cell front surface, and this regional square resistance is not more than 45 Ω/.
9. manufacture method according to claim 1 is characterized in that, electrode was by silver, copper, nickel, tin or contain the alloy composition of above-mentioned element before step (h) was described.
10. manufacture method according to claim 9 is characterized in that, described preceding electrode is positioned on the local heavy doping N type layer.
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