CN103924306A - Texture surface making method for silicon heterojunction solar cells - Google Patents
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Abstract
The invention discloses a texture surface making method for silicon heterojunction solar cells. According to the method disclosed by the invention, a monocrystalline silicon wafer of a solar cell is subjected to a two-step texture surface making process, so that a smooth pyramid structure with a size of 3-10 mu m is formed on the surface of the silicon wafer; metal ion residues on the surface of the silicon wafer are removed, so that the modification on morphology and electrical properties is implemented. The method can be used for effectively reducing the reflectivity of the surface of a silicon wafer in a 400-1200nm wavelength range, thereby improving the output characteristics of cells; the preparation method is simple, and easy to implement.
Description
Technical field
The present invention relates to the manufacture field of silicon heterojunction solar battery, particularly a kind of silicon heterojunction solar battery surface wool manufacturing preparation method and application thereof.
Background technology
Photovoltaic generation is that the internationally recognized solution energy lacks one of effective way with problem of environmental pollution.Silicon heterojunction solar battery because of its efficiency of conversion high, preparation process low power consuming, production cost is comparatively cheap etc., and advantage is subject to extensive concern.Than traditional monocrystalline silicon battery, silicon heterojunction solar battery adopts amorphous silicon thin-film materials as emission layer and passivation layer, have higher open circuit voltage, but amorphous silicon material is as a kind of collimation tape splicing gap material, has larger uptake factor.Therefore,, in order to improve the photoelectric transformation efficiency of battery, just must increase the sunken luminous energy power of battery to improve short-circuit current density.Matte silicon substrate, owing to having good sunken light effect, can obviously improve the short-circuit current of battery.The conventional mineral alkalis such as NaOH can be realized being uniformly distributed of silicon chip surface gold tower to monocrystalline substrate making herbs into wool at present, and pyramid size can be controlled between 5-15 μ m, fall into optical property good.But substrate surface for roughness after its making herbs into wool increases, and has more pyramid spike, makes intrinsic amorphous silicon passivation thin layer be difficult to uniform deposition at monocrystalline silicon surface, deteriorated interface quality.Trimethylammonium hydroxide (TMAH) has been applied to silicon chip surface making herbs into wool as a kind of organic bases.Than NaOH solution, pyramid size after TMAH making herbs into wool is less, the making herbs into wool time is shorter, pattern is more round and smooth, and there is no the residual of metal ion, is more suitable for as boundary defect state being required to the making herbs into wool solvent of strict silicon heterojunction solar battery.But because TMAH solution price is higher at present, be difficult to be widely adopted in suitability for industrialized production.Therefore, explore a kind of meet relatively inexpensive, fall into that light is good, to fall into light method be the key that promotes silicon heterojunction solar battery leather producing process for pattern characteristic good, the residual few monocrystalline substrate of metal ion.
Summary of the invention
The present invention seeks to the problem for above-mentioned existence, by adopting the etching method of NaOH solution and the combination of TMAH solution phase to carry out making herbs into wool to the monocrystalline substrate of silicon heterojunction solar battery.This structure can fall under the prerequisite of luminous energy power at the wide spectrum that guarantees making herbs into wool substrate, and further optimizing metal word tower distribution of sizes, appearance structure and surface property, realize the object that improves battery output characteristic parameter, and its preparation method is cheap simple, easy to implement.
Technical scheme of the present invention:
A silicon heterojunction solar battery etching method, is that monocrystalline substrate is being passed through acetone and each ultrasonic cleaning of ethanolic soln 5min, removes silicon chip surface partial organic substances and metallics and stains.Adopt deionized water rinsing totally afterwards sample to be placed in to 80 ℃ of temperature, concentration is that the affected layer that goes that carries out 10min in the inorganic alkali solution of 1-3% is processed, utilize under high-concentration alkali liquor high temperature the feature of the isotropic etch of silicon chip is removed to the mechanical damage layer that silicon chip surface stays in cutting process, obtain comparatively smooth silicon chip surface, then sample is put into deionized water and rinse after 3min standby.Making herbs into wool process is mainly divided into two steps, and the first step making herbs into wool is mineral alkali, Virahol (IPA) and the NaSiO by containing lower concentration
3solution prepare the relatively large pyramid pattern of size and distribute, utilize low solubility alkali lye to corrode to carry out surface to the anisotropic of monocrystalline silicon piece and carry out texturing, from making herbs into wool solution, take out afterwards, use a large amount of deionized water rinsings.Second step making herbs into wool is that the mixing solutions that sample that the first step making herbs into wool was processed is put into organic bases and IPA carries out making herbs into wool, utilize organic alkali lye to corrode to carry out surface to the anisotropic of silicon single crystal and carry out texturing, make silicon chip surface pyramid more round and smooth and present the topographic profile that large pyramidion is alternate, step as shown in Figure 1.In said process, after the first step making herbs into wool, the gold Sopwith staff of silicon chip surface cun is mainly distributed between 5-12 μ m; After second step making herbs into wool, silicon chip surface pyramid is evenly distributed between 3-10 μ m, and reflectivity obviously reduces.
Wherein in the first step making herbs into wool, mineral alkali can be selected NaOH or KOH, the mineral alkali that each constituent mass concentration is 1-3%, the NaSiO of 0.5-2%
3, 6% Virahol (IPA), making herbs into wool temperature is between 75 ~ 85 ℃, the time is 35min ~ 45min, making herbs into wool finishes the rear deionized water rinsing 3min that uses.
In second step making herbs into wool, organic bases can be any one in Tetramethylammonium hydroxide (TMAH), quadrol, second triamine, methanediamine, TBAH, making herbs into wool temperature is between 75 ~ 85 ℃, the making herbs into wool time regulates between 3min ~ 10min, after making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The type of heating of above-mentioned making herbs into wool solution is the heating of closed waters, also can adopt open-heating mode.The silicon chip of making herbs into wool is that the cutting blade in N-type (100) crystal orientation can be also P type, and the structure of solar cell can be HIT structure, SHJ structure or HBC structure, and the selected substrate of making herbs into wool can be Cz or FZ substrate.
Advantage of the present invention and positively effect:
By in conjunction with mineral alkali making herbs into wool and two kinds of solvents of organic bases to monocrystalline silicon surface making herbs into wool.The first step making herbs into wool utilizes the inorganic alkali lye of low solubility to produce and have the textured surfaces that pyramid distributes monocrystalline silicon surface anisotropic etching.The pyramid size that mineral alkali making herbs into wool produces is larger, long wave incident light is had to good light trapping effect, and inorganic alkali solution price is relatively inexpensive, and the first step adopts inorganic alkali solution making herbs into wool to obtain the cost that suede structure is conducive to reduce substrate making herbs into wool.Second step making herbs into wool is on the basis of the first step making herbs into wool, adopts organic bases as the making herbs into wool of TMAH solution, makes silicon chip surface be evenly distributed with the mutually nested pyramid of size.Because the molecular polarity of the organic bases solution of TMAH is less with respect to mineral alkali, so it more easily adheres at silicon chip surface, concentration is higher, so the time of second step organic bases making herbs into wool is relatively short, and after organic bases making herbs into wool, pyramid size is more round and smooth, and Ta Feng and tower paddy are got rid of by the smoothing effect of organic bases solution.This appearance structure is suitable as the substrate of silicon heterojunction solar battery, can suppress amorphous silicon membrane in its surperficial epitaxy, falls the low electric leakage gully density of battery.In addition, organic bases making herbs into wool design is implemented after mineral alkali making herbs into wool, can be realized the effect of the metal ion pollution producing after clean mineral alkali making herbs into wool, improved the electrology characteristic of making herbs into wool silicon chip surface, and then improved the output characteristic of silicon heterojunction solar battery.
Accompanying drawing explanation
The implementation step schematic diagram of Fig. 1 etching method of the present invention.
The wafer topography figure of Fig. 2 for adopting single step NaOH making herbs into wool to obtain.
The wafer topography figure of Fig. 3 for adopting single step TMAH making herbs into wool to obtain.
The wafer topography figure of Fig. 4 for adopting two step etching method of the present invention to prepare.
Fig. 5 is the silicon chip surface that adopts respectively single step NaOH making herbs into wool, single step TMAH making herbs into wool and two step etching method of the present invention and the prepare reflectance map to different lambda1-wavelengths.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical solutions according to the invention are described in detail.
embodiment 1:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) the first step making herbs into wool: going silicon chip after affected layer to put into strength of solution proportioning is 1% NaOH, 0.5% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 30min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min.
4) second step making herbs into wool: the silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, the TMAH that strength of solution proportioning is 2%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 3min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 1-8 μ m, and the average reflectance between 400nm ~ 1200nm is 14.3%, and silicon chip minority carrier life time is 175 μ s.
embodiment 2:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) the first step making herbs into wool: going silicon chip after affected layer to put into strength of solution proportioning is 3% NaOH, 1% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 40min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min.
4) second step making herbs into wool: the silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, the TMAH that strength of solution proportioning is 2%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 3min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 2-12 μ m, and the average reflectance between 400nm ~ 1200nm is 12.2%, and silicon chip minority carrier life time is 193 μ s.
embodiment 3:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) the first step making herbs into wool: going silicon chip after affected layer to put into strength of solution proportioning is 3% NaOH, 3% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 35min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min.
4) second step making herbs into wool: the silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, the TMAH that strength of solution proportioning is 5%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 4min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 2-7 μ m, and the average reflectance between 400nm ~ 1200nm is 14.8%, and silicon chip minority carrier life time is 167 μ s.
embodiment 4:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) the first step making herbs into wool: going silicon chip after affected layer to put into strength of solution proportioning is 1% NaOH, 1% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 40min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min.
4) second step making herbs into wool: the silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, the TMAH that strength of solution proportioning is 2%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 10min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 4-11 μ m, and the average reflectance between 400nm ~ 1200nm is 13.7%, and silicon chip minority carrier life time is 207 μ s.
embodiment 5:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) going silicon chip after affected layer to put into strength of solution proportioning is 1% NaOH, 1% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 40min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 5-12 μ m, as shown in Figure 2.The average reflectance of substrate between 400nm ~ 1200nm is 16.1%, and silicon chip minority carrier life time is 121 μ s.
embodiment 6:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, and the TMAH that strength of solution proportioning is 2%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 5min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 3-10 μ m, and as shown in Figure 3, the average reflectance between 400nm ~ 1200nm is 12.6%, and silicon chip minority carrier life time is 189 μ s.
embodiment 7:
1) after putting into acetone soln ultrasonic cleaning 5min, takes out the cutting silicon wafer of getting N-type (100) crystal orientation; After deionized water rinsing 3min, put into ethanol solution ultrasonic cleaning 5min, after taking out, use deionized water rinsing 3min.
2) silicon chip having cleaned being put into concentration is 10% NaOH solution, solution temperature is 80 ℃, reaction times is 10min, with glass stick, solution is stirred during this time, emitting of accelerated reaction gas, type of heating is heating in water bath, utilizes the affected layer of under high-concentration alkali liquor high temperature, the feature of the isotropic etch of silicon chip being removed silicon chip surface, obtains comparatively smooth silicon chip surface.Take out afterwards sample, use deionized water rinsing 3min.
3) the first step making herbs into wool: going silicon chip after affected layer to put into strength of solution proportioning is 1% NaOH, 1% NaSiO
3, 6% IPA mixing solutions in, making herbs into wool temperature is between 80 ℃, the making herbs into wool time is at 40min.Utilize low solubility alkali lye to corrode silicon chip surface is carried out to texturing the anisotropic of monocrystalline silicon piece.After making herbs into wool, adopt deionized water rinsing 3min.
4) second step making herbs into wool: the silicon chip after previous step is processed is put into the mixing solutions of TMAH, IPA, the TMAH that strength of solution proportioning is 2%, 10% IPA making herbs into wool temperature are at 80 ℃, and the making herbs into wool time is 5min.Utilize the organic alkali lye of TMAH to corrode silicon chip surface is carried out to texturing the anisotropic of silicon single crystal.After making herbs into wool, adopt deionized water rinsing 3min, adopt afterwards RCA washing out method cleaning silicon chip surface, in order to test.
The prepared monocrystalline silicon suede microstructure size of the present embodiment is distributed between 3-12 μ m, and as shown in Figure 4, the average reflectance between 400nm ~ 1200nm is 11.8%, and silicon chip minority carrier life time is 225 μ s.
The gold tower appearance structure that different making herbs into wool solution making herbs into wool produces can be found out in Fig. 2-4, and this structure directly affects the sunken luminous energy power of silicon chip after making herbs into wool.Fig. 5 is the silicon chip surface that adopts respectively NaOH making herbs into wool, TMAH making herbs into wool and two step etching method of the present invention and the prepare reflectance map to different lambda1-wavelengths.NaOH making herbs into wool and TMAH making herbs into wool are less for the reflectivity of long wave and shortwave respectively as seen from the figure, the silicon chip surface that adopts two step etching methods to prepare all has and better falls into light effect at 400-1200nm wave band, this,, owing to by the respectively modulation of two step leather producing process to silicon chip surface pyramid size, makes it more be conducive to the sunken light of wide spectrum.
To sum up, the invention provides a kind of etching method of silicon heterojunction solar battery, the method and silicon heterojunction solar battery preparation technology are completely compatible, are generally applicable to the preparation of monocrystalline silicon substrate heterojunction solar cell substrate, method cheapness is simply easy to realize, and is convenient to suitability for industrialized production.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (4)
1. a silicon heterojunction solar battery etching method, comprises silicon chip pre-treatment, goes affected layer and two-step approach making herbs into wool, it is characterized in that described silicon chip pretreatment process is for to clean silicon chip surface by the order of acetone-water-dehydrated alcohol-water; The described method of removing affected layer for stir soaking pretreated silicon chip washed with de-ionized water after 10min in the inorganic alkali lye of 1%-3% at 80 ℃; The first step of described two-step approach making herbs into wool is that to put into mass concentration proportioning be the mineral alkali of 1-3%, the NaSiO of 0.5-2% to the silicon chip after affected layer
3, 6% Virahol (IPA) mixing solutions in, at 75 ~ 85 ℃, making herbs into wool 35 ~ 45min, then deionized water rinsing 3min, second step be the silicon chip after the described the first step is processed to put into mass concentration proportioning be the organic bases of 2-5%, the IPA of 9-11%, at 75 ~ 85 ℃, making herbs into wool 3 ~ 10min, then adopt deionized water rinsing 3min, finally adopt RCA washing out method cleaning silicon chip surface.
2. silicon heterojunction solar battery etching method according to claim 1, is characterized in that described monocrystalline substrate is FZ or Cz silicon chip, and doping type is N-type or P type.
3. silicon heterojunction solar battery etching method according to claim 1, is characterized in that described organic bases is a kind of in Tetramethylammonium hydroxide (TMAH), quadrol, second triamine, methanediamine or TBAH.
4. silicon heterojunction solar battery etching method according to claim 1, is characterized in that described mineral alkali is NaOH or KOH.
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CN104562211A (en) * | 2014-12-26 | 2015-04-29 | 横店集团东磁股份有限公司 | Texture surface making method capable of improving conversion efficiency of monocrystal cell |
CN105113013A (en) * | 2015-08-21 | 2015-12-02 | 合肥中南光电有限公司 | Efficient and environment-friendly monocrystalline silicon piece texture surface making liquid and preparation method thereof |
CN113529173A (en) * | 2021-07-14 | 2021-10-22 | 西安蓝桥新能源科技有限公司 | Two-step texturing additive for preparing multilayer pyramid monocrystalline silicon textured surface and application thereof |
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CN113529173B (en) * | 2021-07-14 | 2023-07-28 | 西安蓝桥新能源科技有限公司 | Two-step texturing additive for preparing multi-layer pyramid monocrystalline silicon suede and application thereof |
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