CN109943888A - It is a kind of reduce the black silicon making herbs into wool of polycrystalline after flannelette difference borehole acid additive and its application - Google Patents
It is a kind of reduce the black silicon making herbs into wool of polycrystalline after flannelette difference borehole acid additive and its application Download PDFInfo
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Abstract
The present invention relates to a kind of borehole acid additive of flannelette difference after reduction black silicon making herbs into wool of polycrystalline and its applications, its component are as follows: 0.5~1wt% of ethoxylated dodecyl alcohol, 0.5~1.5wt% of tartaric acid, 0.5~2wt% of sodium alginate, 1~3wt% of aspartic acid, 1~5wt% of triethylene-glycol, 0.5~1wt% of diethylene glycol monomethyl ether, 86.5~96wt% of ultrapure water.The present invention controls hole depth and the aperture of submicron order hole by adjusting the technological parameter of borehole time and pore-enlargement, suede structure and reflectivity is set more to meet the performance requirement of polysilicon solar cell, it is beneficial to subsequent technique and the transfer efficiency for improving polysilicon solar cell.
Description
Technical field
The invention belongs to borehole additive and its application field, in particular to flannelette is poor after a kind of black silicon making herbs into wool of reduction polycrystalline
Different borehole acid additive and its application.
Background technique
In area of solar cell, crystal silicon solar energy battery always in occupation of 85% or more the market share, drop this
The two big targets that effect is crystal silicon solar energy battery are proposed, optical loss directly affects the photoelectric conversion efficiency of solar battery.
The micron order vermicular texture reflectivity that conventional polysilicon silicic acid process for etching is prepared on Buddha's warrior attendant wire cutting polysilicon is higher, black
Silicon may be implemented lower surface reflectivity, make the net of crystal silicon solar energy battery due to having the geometry of submicron order
Efficiency gets a promotion.
Black silicon solar cell mainly uses the polysilicon chip of Buddha's warrior attendant wire cutting to produce, and the black common preparation process of silicon includes
Reactive ion etching method, femtosecond laser etching method, electrochemical etching method and metal catalytic chemical etching method, wherein metal catalytic
Etching method is learned because its preparation process is simple, cost is relatively low, and the advantage compatible with classical acid making herbs into wool producing line is used more and more,
The technique can prepare the black silicon of polycrystalline of submicron order hole.
Since polysilicon chip is the production method using ingot casting formula, the crystal grain on monolithic polysilicon chip is along different crystal faces
Oriented growth forms.The interplanar atomic density of different crystal face growths is different, and the atomic density on (111) solid matter face is larger, changes
It is more stable to learn combination, surface can be relatively low.And the atomic density in (100) and (110) crystal face is relatively sparse, chemistry knot
It is relatively poor to close stability, surface can be relatively high.
Metal catalytic chemical etching method is during borehole, due to (100) crystal plane surface energy highest, so borehole rate is most
Fastly；(110) crystal face borehole rate is taken second place；(111) surface of crystal face can be minimum, and borehole rate is most slow.In this way in different crystal faces
On corrosion rate it is inconsistent, eventually lead to the black silicon face crystalline substance Hua Yanchong of polycrystalline, and due to the area difference of different high preferred orientations
It is not larger, cause the uniformity of submicron order suede structure to be affected.There are color difference, serious shadows after PECVD plated film
The appearance of polycrystalline black silicon solar cell and the overall efficiency of component are rung.
Many document patents disclose the method and performance study for preparing black silicon both at home and abroad, at present metal catalytic chemical etching
Metallic silver is widely used as catalyst in method.Application for a patent for invention US2016/0218229A1 is disclosed using metal auxiliaryization
Etching method is learned to be combined with conventional etching process to prepare black silicon, this method utilize metallic particles in an acidic solution to silicon substrate into
Row isotropism or the etching of basic every colleague have obtained poroid micro-structure.But the patent does not consider polysilicon difference
The surface of crystal orientation crystal grain can be different and lead to etch inhomogeneities and crystalline substance Hua Wenti, to how being controlled by adjusting experiment condition
Making herbs into wool face pattern and silicon wafer reflectivity are not also studied.
Shen Wenzhong etc. deliver article [Solar Energy Material and Solar Cells, 2015,143:
302-310] in prepare the black silicon of nanowire structure on the monosilicon using silver-colored catalytic chemistry etching one-step method, 300~
Average reflectance can be down to 5.77% in the visible-range of 1100nm wave band.Since silicon base uses monocrystalline silicon, cost
It is higher relative to polysilicon, the industrialized production of black silicon solar cell is influenced, so the lower polysilicon of use cost comes
Black silicon solar cell is prepared into one of researcher main direction of studying.
A kind of black silicon making herbs into wool reaming additive of polycrystalline is disclosed in Chinese invention patent application CN106119976A, is prepared
The black silicon reflectivity of polycrystalline 17%~22%.But the patent relates only to pore widening step using additive, does not consider
Silver catalysis etching borehole rate difference on the crystal grain of different orientation is larger in borehole step, affects the uniformity of flannelette.In
State application for a patent for invention CN108193281A discloses a kind of borehole adjuvant by 1.0~2.0% citric acids, 1.0~2.0% fourths
The composition such as glycol, 0.05~0.1% silver nitrate, 0.2~0.5% hydroxyethyl cellulose, the black silicon etching method which uses
For one-step method, black silicon face is relatively flat after the pattern of black silicon flannelette and making herbs into wool are difficult to control in process for etching, and reflectivity is higher.
This patent can preferably control suede structure using two-step method making herbs into wool, reduce the reflectivity of the black silicon totality of polycrystalline, and borehole acid
Help to be formed uniformly nanoscale hole hole structure containing solubilizer in solution additive, it is several in the region reflectivity of different high preferred orientations
Indifference, this noble metal for consuming the silver-plated and separated two-step method making herbs into wool of borehole relative to one-step method are less.
Patent of invention WO2014120830A1, which is disclosed, a kind of prepares suede structure in micron-sized using wet chemistry method
Black silicon structure, this method realizes the control to microcosmic flannelette by way of annealing, but the process process is complicated, at
This is higher, is unfavorable for industrialization.Therefore, it is necessary to find the black silicon preparation that a kind of process flow is simple and flannelette pattern is easily controllable
Method improves the transfer efficiency of solar battery to reduce the reflectivity of battery.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of borehole acid of flannelette difference after reduction black silicon making herbs into wool of polycrystalline
Solution additive overcomes the prior art since the differentiation in different regions of different high preferred orientations is larger, leads to the equal of submicron order suede structure
Even property is affected, to influence the appearance of polycrystalline black silicon solar cell and the defect of component efficiency.
A kind of borehole acid additive of the invention, by weight percentage, component includes: ethoxylated dodecyl alcohol 0.5
~1wt%, 0.5~1.5wt% of tartaric acid, 0.5~2wt% of sodium alginate, 1~3wt% of aspartic acid, triethylene-glycol 1
~5wt%, 0.5~1wt% of diethylene glycol monomethyl ether, 86.5~96wt% of ultrapure water.
Further, it is preferred that the borehole acid additive by weight percentage, component are as follows: ethoxylated dodecyl alcohol
1wt%, tartaric acid 1.2wt%, sodium alginate 0.8wt%, aspartic acid 1wt%, triethylene-glycol 2wt%, diethylene glycol
Monomethyl ether 1wt%, ultrapure water 93wt%.
The borehole acid additive is soluble in acid solution, and easily clean from polysilicon chip surface clean, and pH value is
3.2, on the pH value of borehole acid solution without influence.
Ethoxylated dodecyl alcohol in the borehole acid additive is surfactant, can reduce the table of etching solution
Face tension makes the H for being attached to silicon chip surface2Bubble removing, while the wetability of silicon chip surface can be increased.
The effect of tartaric acid in the borehole acid additive is to adjust the pH value of additive, keeps additive acid,
The acidity to acid etching liquid is avoided to have an impact.
Sodium alginate in the borehole acid additive plays a part of emulsifier and solubilizer, ensure that additive
Stability.The amino in aspartic acid in the borehole acid additive can reduce the surface energy of silicon wafer, especially to low index
The reduction effect of crystal face is extremely obvious, and the surface energy differential for reducing different crystal orientations crystal grain is different, makes the microcellular structure distribution ground of etching
More evenly.The alkyl in triethylene-glycol and diethylene glycol monomethyl ether in the borehole acid additive can adhere to silicon wafer
On, towards in aqueous solution, hydroxyl can form hydrogen bond in aqueous solution and have hydrophily, therefore increase for the hydroxyl of the other end
The wetability of silicon chip surface contacts reaction solution more fully with polysilicon, obtains flannelette more evenly.
A kind of application of borehole acid additive of the invention in the black silicon making herbs into wool of polycrystalline.
A kind of black silicon etching method of polycrystalline of the invention, comprising:
(1) polysilicon is subjected to prerinse, specifically:
Polysilicon is immersed in dense H2SO4(95wt%): H2O2The volume ratio of (30wt%) is to boil in the reaction solution of 3:1
30min is boiled, the organic matter on polysilicon chip surface is removed, then silicon wafer is immersed in dilute HF solution pickling (reaction of 1~5wt%
300s), the oxide layer on polysilicon chip surface is removed；
Wherein H2SO4(95wt%): H2O2The volume ratio of (30wt%) is the reaction solution of 3:1, HF solution respectively resistance to
It is configured in acid-base groove；
(2) alkali polishing treatment:
Polysilicon in step (1) after prerinse is immersed in the aqueous slkali of 8~10wt%, etches 190 at 70~90 DEG C
~230s removes the damaging layer on surface；
Further specifically: configuration concentration is the aqueous slkali of 8~10wt% in acid and alkali-resistance slot, and the aqueous slkali is
KOH or NaOH solution；Then solution is heated to 70~90 DEG C；Polysilicon chip is immersed in above-mentioned aqueous slkali again and reacts 190
~230s, the damaging layer that removal Buddha's warrior attendant wire cutting leaves；
(3) silver-plated process:
Polysilicon after step (2) alkali polishing treatment is immersed in the HF and 1 × 10 of 0.5~0.7wt%-3~5 × 10- 3Wt%AgNO3Mixed reaction solution in deposit 100~130s of Argent grain, using silver ion reduction at the self assembly of nanoparticle
Journey forms the Argent grain reunited on polysilicon chip surface；
The wherein HF of 0.5~0.7wt% and 1 × 10-3~5 × 10-3Wt%AgNO3Mixed reaction solution in acid and alkali-resistance slot
It is configured；
(4) borehole is handled:
Polysilicon after silver-plated process in step (3) is immersed in the borehole etching liquid of the acid additive containing borehole 30
150~300s is etched at a temperature of~40 DEG C to etch to be formed in polysilicon surface and receive using the principle of metal catalytic chemical etching
Meter level hole configurations；Wherein borehole etching liquid is the H that concentration is 9~11wt%2O2, 3~5wt% HF and 0.5~2wt% dig
The mixed reaction solution of hole acid additive；Wherein etch period determines the size of hole depth in borehole technique, and the borehole time gets over
Long hole depth is bigger；
Further specifically: the H of 9~11wt% is configured in acid and alkali-resistance slot2O2It is molten with the HF hybrid reaction of 3~5wt%
Borehole acid additive is added into reaction solution for liquid；Then reaction solution is heated to 30~40 DEG C；Polysilicon chip is submerged again
150~300s is etched in above-mentioned mixed reaction solution；
(5) desilverization is handled:
The H for being 1.5~2wt% by treated polysilicon the is immersed in concentration of borehole in step (4)2O2With 0.75~
The NH of 0.95wt%3·H2In the mixed reaction solution of O, react 180~220s, removal be deposited on polysilicon chip surface and inside
Argent grain；
The wherein H of 1.5~2wt%2O2With the NH of 0.75~0.95wt%3·H2The mixed reaction solution of O is in acid and alkali-resistance slot
Configuration；
(6) expanding treatment:
The HNO for being 24~26wt% by treated polysilicon the is immersed in concentration of the desilverization in step (5)3With 3~5wt%'s
In HF mixed reaction solution, in 9~11 DEG C of temperature 120~180s of reaming, the deep hole formed is expanded, is optimized more
Crystal silicon chip suede structure；Etch period determines the size in aperture in chambering process, and the longer aperture of pore-enlargement is bigger；
Further specifically: the HNO of 24~26wt% is configured in acid and alkali-resistance slot3It is molten with the HF hybrid reaction of 3~5wt%
Liquid；Then reaction solution temperature is controlled at 9~11 DEG C；Polysilicon chip is immersed in reaming in above-mentioned mixed reaction solution again
120~180s carries out expansion modification to the nanoscale deep hole closely formed, optimizes black silicon suede structure；
(7) alkali drift is handled:
Polysilicon after step (6) expanding treatment is immersed in the H that concentration is 1.5~2.5wt%2O2, 0.5~0.7wt%
NH3·H2The KOH mixed reaction solution of O and 3~5wt% reacts 10~30s, and the metastable state that removal silicon chip surface outer layer is formed is more
Pore structure；The wherein H of 1.5~2.5wt%2O2, 0.5~0.7wt% NH3·H2The KOH mixed reaction solution of O and 3~5wt%
It is configured in acid and alkali-resistance slot；
(8) sour drift processing is carried out:
The H for being 5~7wt% by step (7) alkali drift treated polysilicon is immersed in concentration2O2, 6~10wt% HCl and
60s is reacted in the HF mixed reaction solution of 7~11wt%, removes the metal impurities and oxide layer on surface, forms hydrophobic surface.Finally
The submicron order hemispherical that aperture is between 600~1000nm, hole depth is between 300~600nm is formed on polysilicon chip surface
Hole flannelette.
Polysilicon is Buddha's warrior attendant wire cutting polysilicon chip, mortar cutting polysilicon or class monocrystalline silicon piece in the step (1).
Aqueous slkali is KOH or NaOH solution in the step (2).
Each step is required to using ultrapure water cleaning polysilicon chip 30 seconds, so after reaction in step (1)~(8)
Afterwards with dry N2Drying.
The present invention provides a kind of black silicon of polycrystalline of the method preparation.
The aperture of the black silicon of polycrystalline is 600~1000nm, and hole depth is 300~600nm, and polysilicon 300~
The reflectivity of 1000nm wave band is 15%~23%.
The hole is the hemispherical dome structure of similar submicron order, light wave long number of the geometric dimension substantially with generation photovoltaic effect
Magnitude is identical.The present invention provides a kind of application of black silicon of the polycrystalline, such as crystal silicon solar energy battery field.
In the present invention metal catalytic chemical etching method borehole reaction principle as shown in Fig. 2, silver nano-grain catalysis
Under, silicon atom is by H2O2It aoxidizes and is etched by HF and dissolved, generate H2SiF6While also with H2The generation of bubble, it is entire etched
Journey is considered as redox reaction.Wherein Argent grain is catalyst, H2O2Oxidant is made, HF does etching agent.
In borehole step of the present invention, reaction equation is as follows:
Cathode reaction: H2O2+2H++2e-→2H2O
Anode reaction: Si+2H2O→SiO2+4H++4e-
SiO2+6HF→H2SiF6+2H2O
Beneficial effect
(1) compared with prior art, the black silicon of polycrystalline prepared using borehole acid additive of the invention, different orientation are brilliant
Reflectivity on face is close to unanimously, and by adjusting technological parameter, the totality that polysilicon chip can be improved falls into light effect, compared to similar
The black silicon of polycrystalline of additive preparation has lower reflectivity, generally also more preferable to the capture ability of light；
(2) Additive in the present invention reduces the surface energy of silicon wafer, especially to low index crystal plane in silicon chip surface
Reduction effect is extremely obvious, and the surface energy differential for reducing different crystal orientations crystal grain is different, and the micropore for making etching more evenly, reduces simultaneously
The rate of etching makes reaction become slow and controllable, it is easier to more be met black silicon solar electricity by adjusting technological parameter
The micro-structure of pond performance requirement；Under the action of additive, surface tension is substantially reduced acid etching liquid, reacts the H of generation2Gas
Bubble can remove faster, improve the uniformity of reaction, eliminate the generation of spot.Additive and silicon wafer are acted on silicon wafer table
The hydrophobic structure in face becomes hydrophilic-structure, enhances the wetability of silicon chip surface；
(3) the black silicon process of preparing in the invention patent is simple, and cost is relatively low, is suitble to industrialization production；
(4) borehole acid additive ingredient of the invention is more typical chemicals, and low in cost；
(5) additive of the invention can reduce the surface tension of solution, the H for generating etching2Bubble is de- from silicon chip surface
It removes；
(6) additive of the invention can reduce the surface energy of silicon wafer, especially extremely bright to the reduction effect of low index crystal plane
Aobvious, the surface energy differential reduced on different crystal orientations crystal grain is different, and the submicron order suede structure for obtaining etching is more evenly；
(7) additive of the invention can reduce mixed acid solution to the etch rate of silicon wafer, make etching reaction become it is slow and
Controllably；
(8) this additive can enhance the wetability of silicon chip surface, and the hydrophobic structure of silicon chip surface is become hydrophilic-structure, is made
It is more uniform to etch obtained light trapping structure；
(9) present invention by control borehole time and reaming time, can directly control submicron order hole hole depth and
Aperture, the cell morphology for more being met crystal silicon solar energy battery performance requirement (meet suede structure and reflectivity more
The performance requirement of crystal silicon solar batteries) it is beneficial to the transfer efficiency of subsequent technique and raising polysilicon solar cell；
(10) the black silicon making herbs into wool borehole acid additive of polycrystalline provided by, the additive is added in borehole step, disappears
Except silicon wafer crystalline substance Hua Wenti after the black silicon making herbs into wool of polycrystalline, so that the totality of polycrystalline black silicon solar cell is fallen into light effect and is obviously improved,
To improve photoelectric conversion efficiency；The preparation method of black silicon is metal catalytic chemical etching method in the present invention, by walking in borehole
The additive is added in rapid, borehole reaction can be made to become slow and controllable, the reaction rate on different crystal orientations crystal grain is close to one
It causes, and the bubble that reaction can be made to generate removes as soon as possible, reaction solution is more fully contacted with polysilicon chip, finally eliminates polycrystalline
The brilliant Hua Wenti of black silicon.The aperture of the black silicon of polycrystalline and hole depth size are almost the same on the crystal grain of different crystal orientations after making herbs into wool, not only
The appearance uniformity of the black silicon of polycrystalline is improved, and so that the totality of the black silicon of polycrystalline is fallen into light effect and has obtained significantly being promoted.
Detailed description of the invention
Fig. 1 is the 10k times of Flied emission SEM figure of the black silicon face of polycrystalline prepared in the embodiment of the present invention 3；
Fig. 2 is the making herbs into wool schematic illustration of metal catalytic chemical etching method；
Fig. 3 is the black silicon appearance picture of polycrystalline prepared in the embodiment of the present invention 1；
Fig. 4 is the 20k times of Flied emission SEM figure of the black silicon face of polycrystalline prepared in the embodiment of the present invention 1；
Fig. 5 is the 20k times of Flied emission SEM figure of the black silicon section of polycrystalline prepared in the embodiment of the present invention 1；
Fig. 6 is the reflectivity of the black silicon of polycrystalline for preparing in the embodiment of the present invention 1 in 300~1000nm wave band；
Fig. 7 is the black silicon appearance picture of polycrystalline prepared in the embodiment of the present invention 2；
Fig. 8 is the 20k times of Flied emission SEM figure of the black silicon face of polycrystalline prepared in the embodiment of the present invention 2；
Fig. 9 is the 20k times of Flied emission SEM figure of the black silicon section of polycrystalline prepared in the embodiment of the present invention 2；
Figure 10 is the reflectivity of the black silicon of polycrystalline for preparing in the embodiment of the present invention 2 in 300~1000nm wave band；
Figure 11 is the black silicon appearance picture of polycrystalline prepared in the embodiment of the present invention 3；
Figure 12 is the 20k times of Flied emission SEM figure of the black silicon face of polycrystalline prepared in the embodiment of the present invention 3；
Figure 13 is the 20k times of Flied emission SEM figure of the black silicon section of polycrystalline prepared in the embodiment of the present invention 3；
Figure 14 is the reflectivity of the black silicon of polycrystalline for preparing in the embodiment of the present invention 3 in 300~1000nm wave band.
Figure 15 is the reflectivity of the black silicon of polycrystalline for preparing in the embodiment of the present invention 3 in 300~1000nm wave band different zones
Comparison diagram.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.Polysilicon used in this patent is commercialized p-type polysilicon piece, is mixed for boron, and resistivity is 1~3 Ω cm, thick
Degree is 200 ± 10 μm.
Embodiment 1
(1) prewashed specific process step:
Step 1: according to dense H in acid and alkali-resistance slot2SO4(95wt%): H2O2(30wt%) volume ratio is 3:1 configuration reaction
Solution；
Step 2: polysilicon chip is immersed in above-mentioned reaction solution and boils 30min；
Step 3: the HF solution of 2wt% is configured in acid and alkali-resistance slot；
Step 4: polysilicon chip is immersed in above-mentioned HF solution and reacts 300s；
(2) specific process step of alkali rough polishing:
Step 1: configuration concentration is the KOH solution of 9wt% in acid and alkali-resistance slot；
Step 2: solution is heated to 80 DEG C；
Step 3: polysilicon chip is immersed in above-mentioned KOH solution and reacts 210s；
(3) silver-plated specific process step:
Step 1: the HF and 1.4 × 10 of 0.6wt% is configured in acid and alkali-resistance slot-3The AgNO of wt%3Mixed reaction solution；
Step 2: polysilicon chip is immersed in deposition Argent grain 120s in above-mentioned mixed reaction solution；
(4) specific process step of borehole:
Step 1: the H of 10wt% is configured in acid and alkali-resistance slot2O2With the HF mixed reaction solution of 4wt%, no borehole acid solution addition
Agent；
Step 2: reaction solution is heated to 34 DEG C；
Step 3: polysilicon chip is immersed in borehole 150s in above-mentioned reaction；
(5) specific process step of the desilverization:
Step 1: the H of 2wt% is configured in acid and alkali-resistance slot2O2With the NH of 0.85wt%3H2The mixed reaction solution of O；
Step 2: polysilicon chip is immersed in above-mentioned reaction solution and reacts 200s；
(6) specific process step of reaming:
Step 1: the HNO of 26wt% is configured in acid and alkali-resistance slot3With the HF mixed reaction solution of 4wt%；
Step 2: reacting liquid temperature is controlled at 10 DEG C；
Step 3: polysilicon chip is immersed in reaming 140s in above-mentioned reaction solution；
(7) specific process step of alkali drift:
Step 1: the H of 2wt% is configured in acid and alkali-resistance slot2O2, 0.7wt% NH3H2The KOH hybrid reaction of O and 5wt%
Liquid；
Step 2: polysilicon chip being immersed in above-mentioned reaction solution and reacts 15s, and the metastable state that removal silicon chip surface is formed is more
Hole silicon；(8) specific process step of acid drift:
Step 1: the H of 6.8wt% is configured in acid and alkali-resistance slot2O2, 8wt% HCl and 8.5wt% HF mixed reaction solution；
Step 2: polysilicon chip being immersed in above-mentioned reaction solution and reacts 60s, removes the metal impurities and oxide layer on surface,
Form hydrophobic surface.
The appearance photo for finally obtaining the black silicon of polycrystalline is as shown in Figure 3, it can be seen that the preparation of borehole acid additive is not used
The black silicon wafer of polycrystalline spend seriously, the interplanar color difference of different orientation is larger.As shown in figure 4, forming sub-micro on polysilicon chip surface
Meter level meter level hemisphere flannelette, aperture is between 600~850nm.As shown in figure 5, hole depth is between 300~600nm.Such as Fig. 6 institute
Show, the average reflectance in the visible-range of 300~1000nm wavelength is 18.33%.
Embodiment 2
On the basis of embodiment 1, difference is:
In the specific process step of the borehole, borehole etching liquid by 10wt% H2O2, 4wt% HF and 1wt%
Borehole acid additive composition；
The borehole acid additive by weight percentage, component are as follows: ethoxylated dodecyl alcohol 1wt%, tartaric acid
1.2wt%, sodium alginate 0.8wt%, aspartic acid 1wt%, triethylene-glycol 2wt%, diethylene glycol monomethyl ether 1wt%,
Ultrapure water 93wt%.
The appearance photo for finally obtaining the black silicon of polycrystalline is as shown in Figure 7, it can be seen that is added using the black silicon making herbs into wool borehole of polycrystalline
Add agent that can effectively improve brilliant Hua Wenti, the interplanar color difference of different orientation is smaller, and flannelette is uniform.As shown in figure 8, in polycrystalline
Silicon chip surface forms submicron order meter level hemispherical flannelette, and aperture is between 600~800nm.As shown in figure 9, hole depth 300~
Between 550nm.As shown in Figure 10, the average reflectance in the visible-range of 300~1000nm wavelength is 22.45%.
Embodiment 3
On the basis of embodiment 2, difference is:
In the specific process step of the borehole, the borehole time is 180s；
In the specific process step of the reaming, pore-enlargement 160s.
The finally obtained black silicon appearance of polycrystalline is as shown in figure 11, can be effective using the black silicon making herbs into wool borehole additive of polycrystalline
Solution polysilicon making herbs into wool after crystalline substance Hua Wenti, flannelette indifference on the crystal grain of different crystal orientations.As shown in figure 12, pass through embodiment 3
The black silicon face SEM figure of the polycrystalline of preparation can be seen that the aperture of the black silicon of polycrystalline after making herbs into wool between 650~850nm.As shown in figure 13,
The black silicon section SEM figure of the polycrystalline prepared by embodiment 3 can be seen that the hole depth of submicron order between 350~600nm.Such as
Shown in Figure 14, average reflectance of the black silicon of polycrystalline prepared by embodiment 3 in 300~1000nm wave band is 17.78%.
Embodiment 2 and the comparison of embodiment 1 can be seen that using the black silicon dimmer appearance after the making herbs into wool of borehole acid additive,
Crystalline substance flower problem is resolved.Under identical process for etching Parameter Conditions, after borehole acid additive, black silicon suede structure
It shoals, average reflectance increases 4.12%, and borehole reaction becomes slow and controllable.
Embodiment 3 and the comparison of embodiment 2 can be seen that after extending 30s in the reaction time in borehole step, and correspondence is more
Average hole depth will increase about 50nm after crystal silicon chip making herbs into wool.In pore widening step, after 20s will be extended in the reaction time, corresponding polycrystalline
Average pore size will increase about 50nm after silicon wafer wool making.The reflectivity of the black silicon of finally obtained polycrystalline is compared, embodiment 3 is averaged
The average reflectance of luminance factor embodiment 2 low 4.67%.Illustrate can by control borehole step reaction time and reaming
The reaction time of step effectively controls aperture and the hole depth of the black silicon submicron order flannelette of polycrystalline, so that it is black to reach control polycrystalline
The purpose of silicon reflectivity makes the pattern of flannelette and reflectivity more meet the performance requirement of polycrystalline black silicon solar cell, increases more
The transfer efficiency of brilliant black silicon solar cell.
As shown in figure 15, the reflectivity of 6 different zones is measured on the black silicon of polycrystalline prepared by embodiment 3,300~
Almost indifference illustrates different high preferred orientations near 17.78% to the reflectivity of different orientation crystal face in 1000nm wave band
Region making herbs into wool is uniform, and overall sunken light effect is preferable.The black silicon face of polycrystalline of Chinese invention patent application CN108193281A preparation
More smooth, reflectivity is higher, this is also the disadvantage of one-step method making herbs into wool, and the black silicon of polycrystalline of the invention patent preparation has lower hair
Rate is penetrated, submicron order suede structure matches with subsequent surface passivation technology, and uniform suede structure and lower reflection
The conversion effect of solar battery can be improved in rate.
Claims (10)
1. a kind of borehole acid additive, which is characterized in that by weight percentage, component includes: ethoxylated dodecyl alcohol 0.5
~1wt%, 0.5~1.5wt% of tartaric acid, 0.5~2wt% of sodium alginate, 1~3wt% of aspartic acid, triethylene-glycol 1
~5wt%, 0.5~1wt% of diethylene glycol monomethyl ether, 86.5~96wt% of ultrapure water.
2. a kind of application of the borehole acid additive described in claim 1 in the black silicon making herbs into wool of polycrystalline.
3. a kind of black silicon etching method of polycrystalline, comprising:
(1) polysilicon is subjected to prerinse；
(2) alkali polishing treatment:
Polysilicon in step (1) after prerinse is immersed in the aqueous slkali of 8~10wt%, at 70~90 DEG C etch 190~
230s；
(3) silver-plated process:
Polysilicon after step (2) alkali polishing treatment is immersed in the HF and 1 × 10 of 0.5~0.7wt%-3~5 × 10-3Wt%
AgNO3Mixed reaction solution in deposit 100~130s of Argent grain；
(4) borehole is handled:
Polysilicon after silver-plated process in step (3) is immersed in the borehole etching liquid of the acid additive containing borehole, 30~
150~300s is etched at a temperature of 40 DEG C；Wherein borehole etching liquid is the H that concentration is 9~11wt%2O2, 3~5wt% HF and
The mixed reaction solution of 0.5~2wt% borehole acid additive；
(5) desilverization is handled:
The H for being 1.5~2wt% by treated polysilicon the is immersed in concentration of borehole in step (4)2O2With 0.75~0.95wt%
NH3·H2In the mixed reaction solution of O, 180~220s is reacted, removal is deposited on the Argent grain on polysilicon chip surface and inside；
(6) expanding treatment:
The HNO for being 24~26wt% by treated polysilicon the is immersed in concentration of the desilverization in step (5)3It is mixed with the HF of 3~5wt%
It closes in reaction solution, in 9~11 DEG C of 120~180s of temperature reaming；
(7) alkali drift is handled；
(8) sour drift processing is carried out.
4. etching method according to claim 3, which is characterized in that polysilicon is that Buddha's warrior attendant wire cutting is more in the step (1)
Crystal silicon chip, mortar cutting polysilicon or class monocrystalline silicon piece.
5. etching method according to claim 3, which is characterized in that the additive amount of borehole additive accounts in the step (4)
0.5~2wt% of borehole etching liquid quality.
6. etching method according to claim 3, which is characterized in that each step is after reaction in step (1)~(8)
It is required to clean polysilicon chip 30s using ultrapure water, then with dry N2Drying.
7. a kind of black silicon of polycrystalline of claim 3 the method preparation.
8. the black silicon of polycrystalline according to claim 7, which is characterized in that the aperture of the black silicon of polycrystalline is 600~1000nm,
Hole depth be 300~600nm, and polysilicon 300~1000nm wave band reflectivity 15%~23%.
9. the black silicon of polycrystalline according to claim 8, which is characterized in that the hole is the hemispherical dome structure of submicron order.
10. a kind of application of the black silicon of polycrystalline described in claim 7.
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