Embodiment
Prior art forms matte by acid or alkaline etching at silicon chip surface, to strengthen the absorption of silicon chip to the incident sunlight, improves the density of photogenerated current.For solar cell, desirable matte should be evenly big or small, tight between each suede structure, and promptly coverage rate reaches 100%.But the formation of desirable quality matte has been subjected to all multifactor influences, the surface state before for example silicon chip is corroded, the composition of Woolen-making liquid, each components contents, temperature, reaction time etc.And in actual production, complicated more to the influencing factor of this technical process, the variation of each component etc. in the quantity, product of for example processing silicon chip gathering in solution, the Woolen-making liquid.Generally speaking, it is often very high to the requirement of technology controlling and process to form matte by etching method, and quality of stability also be cannot say for sure to demonstrate,prove.
Because the development of thin film deposition processes now is quite ripe, the inventor attempts forming coarse film by depositing operation at silicon chip surface, to substitute " matte " technology, and with the ions diffusion process integration in the follow-up solar cell manufacture process, thereby both formed the coarse battery surface that can reduce reflectivity, formed PN junction again simultaneously.In some practices, the inventor attempts realizing forming coarse battery surface by the processing step of ions diffusion, formation rough polysilicon film and high annealing successively and reaches the purpose that forms PN junction in silicon chip.But find that in subsequent analysis though high annealing can produce the upwards diffusion of ion, to form PN junction in silicon chip, upwards the process of diffusion cannot say for sure to demonstrate,prove doping content final in the silicon chip, thereby may produce higher contact resistance.In addition, high annealing makes that also the junction depth of formed PN junction is darker, is unfavorable for making full use of the light induced electron that photoelectric effect produces.Therefore, the inventor has proposed a kind of manufacture method of the PN junction of more optimizing by repeatedly practising and proving repeatedly.
With reference to shown in Figure 1, the process that forms PN junction in a kind of execution mode of the manufacture method of solar cell of the present invention comprises:
Step s1 forms coarse polysilicon layer at the silicon chip sensitive surface;
Step s2 carries out ions diffusion to the sensitive surface of silicon chip with described coarse polysilicon layer;
Step s3 keeps the passivation reaction thing that forms in the ions diffusion process.
In the above-mentioned execution mode, described coarse polysilicon is owing to be on the sensitive surface of silicon chip, and when illumination was mapped to the sensitive surface of described silicon chip, the reflectivity of light on described coarse polysilicon layer will reduce significantly.And, suppressed the recombination rate in hole and electronics in the solar cell photoelectric transfer process by keeping the passivation reaction thing that forms in the ions diffusion process, thus increased opto-electronic conversion and the electric current that obtains, improved light utilization efficiency.
And because the process of above-mentioned execution mode is to spread after forming polysilicon layer earlier, the process nature of its diffusion be foreign ion along described coarse polysilicon layer surface to the silicon chip diffusion inside, thereby after diffusion, need not to carry out again high annealing, thereby the junction depth of formed PN junction reduces, and has improved the light utilization efficiency of solar cell.
Alternatively, the coarse polysilicon layer of described formation adopts the method for chemical vapour deposition (CVD) or plasma reinforced chemical vapour deposition (PECVD), adopts SiH
4As reacting gas, the temperature of reaction is 500~620 ℃.
Alternatively, the thickness of described coarse polysilicon layer is 200~1000
Alternatively, described silicon chip is a P type silicon chip, the sensitive surface of silicon chip with described coarse polysilicon layer is carried out ions diffusion comprise: at POCl
3, N
2, O
2Atmosphere in carry out ions diffusion, the temperature during diffusion is 700~1000 ℃.
Below give an example, be described in detail with manufacture method to above-mentioned solar cell by the manufacture process of a concrete solar cell.
With reference to shown in Figure 2, a kind of embodiment of the manufacture method of solar cell of the present invention comprises:
Step s101, cleaning silicon wafer.Because in order to save cost, increase the recycling of silicon chip, the silicon chip that is used to make solar cell may be the scrap silicon that originally will abandon, thereby before making solar cell, at first need silicon chip is cleaned, to remove its surperficial pollutant, impurity etc.Clean method commonly used can adopt that machinery sandblasts, a kind of or its combination in the chemical cleaning.Cleaning course in this example comprises and sandblasting and two steps of chemical cleaning.Silicon chip in this example is a P type silicon chip.
Step s102, low temperature drying.After the chemical cleaning of step s101, silicon chip is carried out low temperature drying.Common way is to use N
2Cold wind dries up.
Step s103 forms coarse polysilicon layer at the silicon chip sensitive surface.In this example with SiH
4As reacting gas, the method by chemical vapour deposition (CVD) or plasma reinforced chemical vapour deposition (PECVD) forms coarse polysilicon layer at the sensitive surface of silicon chip.The temperature of reaction can be 500~620 ℃.The thickness of formed rough polysilicon layer can be 200~1000
In described reaction temperature, particularly under 568 ± 2 ℃ the temperature, the polysilicon of deposition will form chondritic, thereby make the surface very coarse.
Step s104 carries out ions diffusion to the sensitive surface of silicon chip with described coarse polysilicon layer.After forming coarse polysilicon layer, described silicon chip with rough polysilicon layer is placed POCl
3, N
2Or POCl
3, N
2, O
2Atmosphere (diffuse source) in, the sensitive surface of described silicon chip is carried out ions diffusion, the temperature during diffusion is 700~1000 ℃.In the described diffusion process, pass through POCl
3With the silicon chip reaction, obtain phosphorus atoms.Through certain hour, phosphorus atoms from around enter the superficial layer of silicon chip sensitive surface, and spread to the silicon chip internal penetration by the space between the silicon atom, formed the interface of N type semiconductor and P type semiconductor, just PN junction.
And in the diffusion process of step s104, the doped polycrystalline silicon layer surface can form the phosphorus glass of thin layer.In the present embodiment, need to keep formed thin layer phosphorus glass.Its reason is as follows: when solar cell carries out opto-electronic conversion, can produce a large amount of holes and electronics.Will produce electric current via flowing of hole and electronics.In case and hole and electron recombination then are equivalent to hole and electronics consume mutually, it can't produce electric current.Therefore, for increasing the electric current that opto-electronic conversion obtains, just should reduce the recombination rate of hole and electronics.And the thin layer phosphorus glass that forms in the described ions diffusion process exactly can suppress the compound of hole and electronics through experiment confirm.Therefore, by keeping formed thin layer phosphorus glass, can reduce described recombination rate in the present embodiment, thereby help increasing the electric current that opto-electronic conversion obtains, improve light utilization efficiency.
Step s105, edge insulation is handled.Because in the diffusion process of step s104, the edge of silicon chip also spreads inevitably goes up phosphorus, so, the positive collected light induced electron of PN junction can have the zone of phosphorus to flow to the back side of PN junction along the edge diffusion, causes short circuit.Therefore, must remove the zone that phosphorus is gone up in the silicon chip edge diffusion, to avoid the generation of short-circuit conditions.Common way is to adopt CF4 to remove.
Step s106 forms anti-reflecting layer at described rough polysilicon laminar surface.Described anti-reflecting layer adopts the reflection coefficient materials with smaller usually, for example silica or silicon nitride.Described anti-reflecting layer can form at described rough polysilicon laminar surface by the method for plasma reinforced chemical vapour deposition.
Step s107, silk screen printing.Solar cell has formed PN junction through after the above-mentioned technology, can produce electric current under illumination, derives for the electric current that will produce, and need make positive and negative two electrodes on battery surface.Silk screen printing is to make the most general a kind of production technology of solar cel electrode at present.Silk screen printing is to use screen process press, on two surfaces (battery front side and the back side) of silicon chip, print three parts by the printing of cell backside silver aluminium paste, the printing of cell backside aluminium paste and cell front side silver paste and form by this technology with predetermined graphic printing for the mode of employing impression.Between each several part technology by low temperature drying make printed pattern more firm attachment in silicon chip surface.
Its operation principle is: utilize silk screen visuals mesh to see through slurry, apply certain pressure with scraper at the slurry position of silk screen, move towards the silk screen other end simultaneously.Printing ink is expressed on the silicon chip surface from the mesh of visuals by scraper in moving.Because the viscous effect of slurry makes the trace set within the specific limits, the printing middle scraper is linear with screen printing forme and silicon chip surface all the time and contact, and contact wire moves with scraper and mobile, thereby finishes print stroke.
Step s108, sintering.Silicon chip through after the silk screen printing can not directly use, and needs through the sintering furnace Fast Sintering organic binder resin to be burnt, and is remaining almost pure, because nature of glass effect and the silver electrode of driving fit on silicon chip.When silver electrode and crystalline silicon when temperature reaches eutectic temperature, the crystalline silicon atom is dissolved in certain proportion in the silver electrode material of fusion and is gone, thereby form the ohmic contact of upper/lower electrode, improve open circuit voltage and two key parameters of fill factor, curve factor of battery sheet, make it have resistance characteristic, to improve the conversion efficiency of battery sheet.
Sintering furnace is divided into presintering, sintering, cooling cooling three phases.Presintering stage purpose is to make the polymer binder in the slurry decompose, burn, and this phase temperature slowly rises; Sintering is finished various physical-chemical reactions in the sintered body in the stage, form the resistive film structure, makes it really have resistance characteristic, and this phase temperature reaches peak value; The cooling cooling stage, the glass cools sclerosis is also solidified, and the resistive film structure is adhered on the silicon chip regularly.
Through the solar cell that the foregoing description is made, its photoelectric conversion efficiency is 15.525%.Thereby with respect to the solar cell of prior art, its light utilization efficiency is greatly improved.
In sum, the manufacture method of solar cell of the present invention adopts in the technology that forms PN junction and forms the rough polysilicon layer earlier, carries out the method for ions diffusion again, and keeps the passivation reaction thing that forms in the ions diffusion process.By on silicon chip, forming coarse polysilicon layer, reduced solar cell to the reflection of light rate, and by keeping the passivation reaction thing that forms in the ions diffusion process, the recombination rate that has suppressed hole and electronics in the solar cell photoelectric transfer process, thereby the electric current that has increased opto-electronic conversion and obtained has improved light utilization efficiency.And, with respect to the technology of acid or alkaline etching formation matte, the quality and the stability of the manufacture method technology more easy to control of above-mentioned solar cell.
Though the present invention discloses as above with preferred embodiment, the present invention is defined in this.Any those skilled in the art without departing from the spirit and scope of the present invention, all can do various changes and modification, so protection scope of the present invention should be as the criterion with claim institute restricted portion.